Electronic structure and NH-tautomerism of a novel metal-free phenanthroline-annelated phthalocyanine
- Martynov, Alexander G, Mack, John, Ngoy, Bokolombe P, Nyokong, Tebello, Gorbunova, Yulia G, Tsivadze, Aslan Yu
- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2017
- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2017
Enantioselective electrochemical carbon-chloride bond cleavage of hexachlorocyclohexanes (HCHs) catalyzed by Mn (III) Cl-phthalocyanine
- Wen, Junxia, Yu, Baoqui, Huang, Tingting, Mack, John, Wildervanck, Martijn, Nyokong, Tebello, Li, Minzhi, Zhu, Weihua, Liang, Xu
- Authors: Wen, Junxia , Yu, Baoqui , Huang, Tingting , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189252 , vital:44831 , xlink:href="https://doi.org/10.1016/j.jelechem.2017.09.020"
- Description: A lipophilic and electron-rich metallophthalocyanine Mn(III)Cl(α,α′-n-OC5H11)8Pc has been synthesized and characterized. A series of electrochemical experiments demonstrate that the Mn(III)Cl(α,α′-n-OC5H11)8Pc complex can be used as a catalyst for highly efficient carbon-chloride bond cleavage of environmental toxic hexachlorocyclohexanes (HCHs) through electrochemical catalysis, and that the increased catalytic efficiency is related to the enantiomeric carbon-chloride σ-bond of HCHs.
- Full Text:
- Date Issued: 2017
- Authors: Wen, Junxia , Yu, Baoqui , Huang, Tingting , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189252 , vital:44831 , xlink:href="https://doi.org/10.1016/j.jelechem.2017.09.020"
- Description: A lipophilic and electron-rich metallophthalocyanine Mn(III)Cl(α,α′-n-OC5H11)8Pc has been synthesized and characterized. A series of electrochemical experiments demonstrate that the Mn(III)Cl(α,α′-n-OC5H11)8Pc complex can be used as a catalyst for highly efficient carbon-chloride bond cleavage of environmental toxic hexachlorocyclohexanes (HCHs) through electrochemical catalysis, and that the increased catalytic efficiency is related to the enantiomeric carbon-chloride σ-bond of HCHs.
- Full Text:
- Date Issued: 2017
Evolution of foraging behaviour: Deep intra-generic genetic divergence between territorial and non-territorial southern African patellid limpets
- Mmonwa, Kolobe L, Teske, Peter R, McQuaid, Christopher D, Barker, Nigel P
- Authors: Mmonwa, Kolobe L , Teske, Peter R , McQuaid, Christopher D , Barker, Nigel P
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/444798 , vital:74299 , https://doi.org/10.1016/j.ympev.2017.05.024
- Description: Southern Africa is a biodiversity hotspot of patellid limpets, with three genera (Helcion, Cymbula and Scutellastra) identified and described in the region. Scutellastra is the most diverse and most frequently studied of these and, along with Cymbula, includes species with territorial and non-territorial foraging behaviours. We used three mitochondrial markers (12S rRNA, 16S rRNA and COI) and one nuclear marker (ATPSβ intron) to assess evolutionary relationships among species of Cymbula and Scutellastra with these two foraging behaviours and to identify which foraging mode is the more ancient. Maximum Likelihood and Bayesian Inference phylogenetic analyses revealed that the species sharing a foraging type are monophyletic in both genera. Territoriality is a derived character, as the clades with this foraging type are nested within a tree that otherwise comprises non-territorial taxa. These include Helcion, which was recovered as sister to the Cymbula/Scutellastra clade, and the next basal genus, Patella, which is ancestral to all southern African patellogastropods. Deep genetic divergence between the two foraging traits reflects strong adaptive effects of resource partitioning in the evolution of southern African patellid limpets.
- Full Text:
- Date Issued: 2017
- Authors: Mmonwa, Kolobe L , Teske, Peter R , McQuaid, Christopher D , Barker, Nigel P
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/444798 , vital:74299 , https://doi.org/10.1016/j.ympev.2017.05.024
- Description: Southern Africa is a biodiversity hotspot of patellid limpets, with three genera (Helcion, Cymbula and Scutellastra) identified and described in the region. Scutellastra is the most diverse and most frequently studied of these and, along with Cymbula, includes species with territorial and non-territorial foraging behaviours. We used three mitochondrial markers (12S rRNA, 16S rRNA and COI) and one nuclear marker (ATPSβ intron) to assess evolutionary relationships among species of Cymbula and Scutellastra with these two foraging behaviours and to identify which foraging mode is the more ancient. Maximum Likelihood and Bayesian Inference phylogenetic analyses revealed that the species sharing a foraging type are monophyletic in both genera. Territoriality is a derived character, as the clades with this foraging type are nested within a tree that otherwise comprises non-territorial taxa. These include Helcion, which was recovered as sister to the Cymbula/Scutellastra clade, and the next basal genus, Patella, which is ancestral to all southern African patellogastropods. Deep genetic divergence between the two foraging traits reflects strong adaptive effects of resource partitioning in the evolution of southern African patellid limpets.
- Full Text:
- Date Issued: 2017
Exploiting Click Chemistry for the Covalent Immobilization of Tetra (4-Propargyloxyphenoxy) Metallophthalocyanines onto Phenylazide-Grafted Gold Surfaces
- Mwanza, Daniel, Mvango, Sindisiwe, Khene, Samson M, Nyokong, Tebello, Mashazi, Philani N
- Authors: Mwanza, Daniel , Mvango, Sindisiwe , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189177 , vital:44824 , xlink:href="https://doi.org/10.1016/j.electacta.2017.09.115"
- Description: In this study, tetra-(4-propargyloxy)phenoxy phthalocyanines (MTPrOPhOPc) were covalently immobilized as thin films onto gold surfaces via click reaction. The gold electrode surfaces were pre-functionalized with phenylazide (Au-PAz) thin film using in-situ diazonium generation followed by electrografting. Copper (I) catalyzed alkynyl-azide cycloaddition (CuCAAC) reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. Au-PAz-MTPrOPhOPc exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and spectroscopic surface characterization of the functionalized gold electrode surfaces confirmed the presence of the phenylazide and MTPrOPhOPc thin monolayer films. The excellent electroanalysis of hydrogen peroxide with the limit of detection (LoD) and limit of quantification (LoQ) in the μM range was obtained. The electrocatalytic reduction peaks for H2O2 were observed at −0.37 V for Au-PAz-Mn(OAc)TPrOPhOPc and −0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-Mn(OAc)TPrOPhOPc and Au-PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution.
- Full Text:
- Date Issued: 2017
- Authors: Mwanza, Daniel , Mvango, Sindisiwe , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189177 , vital:44824 , xlink:href="https://doi.org/10.1016/j.electacta.2017.09.115"
- Description: In this study, tetra-(4-propargyloxy)phenoxy phthalocyanines (MTPrOPhOPc) were covalently immobilized as thin films onto gold surfaces via click reaction. The gold electrode surfaces were pre-functionalized with phenylazide (Au-PAz) thin film using in-situ diazonium generation followed by electrografting. Copper (I) catalyzed alkynyl-azide cycloaddition (CuCAAC) reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. Au-PAz-MTPrOPhOPc exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and spectroscopic surface characterization of the functionalized gold electrode surfaces confirmed the presence of the phenylazide and MTPrOPhOPc thin monolayer films. The excellent electroanalysis of hydrogen peroxide with the limit of detection (LoD) and limit of quantification (LoQ) in the μM range was obtained. The electrocatalytic reduction peaks for H2O2 were observed at −0.37 V for Au-PAz-Mn(OAc)TPrOPhOPc and −0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-Mn(OAc)TPrOPhOPc and Au-PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution.
- Full Text:
- Date Issued: 2017
Exports, capital formation and economic growth in South Africa
- Feddersen, Maura, Nel, Hugo, Botha, Ferdi
- Authors: Feddersen, Maura , Nel, Hugo , Botha, Ferdi
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/396035 , vital:69145 , xlink:href="https://www.ajol.info/index.php/aref/article/view/162150"
- Description: In South Africa the export sector is frequently accorded a special role in encouraging faster economic growth. Nonetheless, a question that remains unresolved is whether higher export growth indeed leads to higher economic growth and what particular role exports may play within the overall economic growth process of the country. This study applies Johansen’s cointegration procedure, impulse response functions, variance decomposition analysis and Granger causality tests to shed light on the channels through which export growth may impact South Africa’s economic growth rate. Quarterly time series data ranging from 1975q1 to 2012q4 is employed in the study’s empirical tests. The results support the notion that the role of exports lies in their ability to encourage investment and capital formation. While export growth directly supports higher economic growth in the short-run, the long-term effect was found to lie in supporting faster capital formation, and in turn, significantly increasing economic growth. Overall, a strategy of export-led growth that does not explicitly emphasize the export-capital-growth connection is likely to fall short of reflecting the dynamics contained within the exports-growth relationship in South Africa.
- Full Text:
- Date Issued: 2017
- Authors: Feddersen, Maura , Nel, Hugo , Botha, Ferdi
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/396035 , vital:69145 , xlink:href="https://www.ajol.info/index.php/aref/article/view/162150"
- Description: In South Africa the export sector is frequently accorded a special role in encouraging faster economic growth. Nonetheless, a question that remains unresolved is whether higher export growth indeed leads to higher economic growth and what particular role exports may play within the overall economic growth process of the country. This study applies Johansen’s cointegration procedure, impulse response functions, variance decomposition analysis and Granger causality tests to shed light on the channels through which export growth may impact South Africa’s economic growth rate. Quarterly time series data ranging from 1975q1 to 2012q4 is employed in the study’s empirical tests. The results support the notion that the role of exports lies in their ability to encourage investment and capital formation. While export growth directly supports higher economic growth in the short-run, the long-term effect was found to lie in supporting faster capital formation, and in turn, significantly increasing economic growth. Overall, a strategy of export-led growth that does not explicitly emphasize the export-capital-growth connection is likely to fall short of reflecting the dynamics contained within the exports-growth relationship in South Africa.
- Full Text:
- Date Issued: 2017
Facile synthesis of glutathione-l-Cysteine co-capped CdTe core shell system
- Daramola, Olamide A, Siwe-Noundou, Xavier, Krause, Rui W M, Marks, John A
- Authors: Daramola, Olamide A , Siwe-Noundou, Xavier , Krause, Rui W M , Marks, John A
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/195003 , vital:45518 , xlink:href="https://doi.org/10.1166/jnn.2017.13823"
- Description: Semiconductor nanoparticles also known as quantum dots (QDs) have been used in diverse areas of application due to their good optical and photo-physical properties. The synthesis of core–shell QDs have assisted to improve the stability of most nano-particles but the size and long term stability of such materials have been problematic. However, thiol-capped CdTe QDs have been regarded as some of the most widely synthesized nanoparticles due to their unique optical properties. The use of un-stable tellurium source such as NaHTe or highly toxic H2Te gas makes the reaction condition cumbersome. In this study, we prepared some CdTe QDs and core–shell QDs using K2TeO3 as a stable source of tellurium without inert gas protection. This was done using a co-capped bio-compatible coating such as cysteine and glutathione following a modified standard method to produce QDs in the yields of about 60 to 80%. All the synthesized materials were subsequently characterized using various characterization techniques. The systematic optimization of the reaction parameters such as reaction time, pH and mole ratio results with a drastic red shift in wavelength (546–600 nm) by the CdTe core proved that an extra material has been deposited unto the surface of the CdTe core. The 60 days stability test conducted demonstrated that the core–shell nanoparticles were quite stable. Since this reaction was performed under open air conditions and no special ligand or buffer solution was used, it may suitably be applied on an industrial scale.
- Full Text:
- Date Issued: 2017
- Authors: Daramola, Olamide A , Siwe-Noundou, Xavier , Krause, Rui W M , Marks, John A
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/195003 , vital:45518 , xlink:href="https://doi.org/10.1166/jnn.2017.13823"
- Description: Semiconductor nanoparticles also known as quantum dots (QDs) have been used in diverse areas of application due to their good optical and photo-physical properties. The synthesis of core–shell QDs have assisted to improve the stability of most nano-particles but the size and long term stability of such materials have been problematic. However, thiol-capped CdTe QDs have been regarded as some of the most widely synthesized nanoparticles due to their unique optical properties. The use of un-stable tellurium source such as NaHTe or highly toxic H2Te gas makes the reaction condition cumbersome. In this study, we prepared some CdTe QDs and core–shell QDs using K2TeO3 as a stable source of tellurium without inert gas protection. This was done using a co-capped bio-compatible coating such as cysteine and glutathione following a modified standard method to produce QDs in the yields of about 60 to 80%. All the synthesized materials were subsequently characterized using various characterization techniques. The systematic optimization of the reaction parameters such as reaction time, pH and mole ratio results with a drastic red shift in wavelength (546–600 nm) by the CdTe core proved that an extra material has been deposited unto the surface of the CdTe core. The 60 days stability test conducted demonstrated that the core–shell nanoparticles were quite stable. Since this reaction was performed under open air conditions and no special ligand or buffer solution was used, it may suitably be applied on an industrial scale.
- Full Text:
- Date Issued: 2017
First example of nonlinear optical materials based on nanoconjugates of sandwich phthalocyanines with quantum dots
- Oluwole, David O, Yagodin, Alexey V, Mkhize, Nhlakanipho C, Sekhosana, Kutloana E, Martynov, Alexander G, Gorbunova, Yulia G, Tsivadze, Aslan Yu, Nyokong, Tebello
- Authors: Oluwole, David O , Yagodin, Alexey V , Mkhize, Nhlakanipho C , Sekhosana, Kutloana E , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238014 , vital:50577 , xlink:href="https://doi.org/10.1002/chem.201604401"
- Description: We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A3B-type phthalocyanine ligand (2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker EuIII octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm−2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.
- Full Text:
- Date Issued: 2017
- Authors: Oluwole, David O , Yagodin, Alexey V , Mkhize, Nhlakanipho C , Sekhosana, Kutloana E , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238014 , vital:50577 , xlink:href="https://doi.org/10.1002/chem.201604401"
- Description: We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A3B-type phthalocyanine ligand (2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker EuIII octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm−2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.
- Full Text:
- Date Issued: 2017
Flexible Metal–Porphyrin Dimers (M= MnIIICl, CoII, NiII, CuII)
- Li, Minzhi, Zhang, Qian, Xu, Li, Zhu, Weihua, Mack, John, May, Aviwe K, Nyokong, Tebello, Kobayashi, Nagao, Liang, Xu
- Authors: Li, Minzhi , Zhang, Qian , Xu, Li , Zhu, Weihua , Mack, John , May, Aviwe K , Nyokong, Tebello , Kobayashi, Nagao , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239676 , vital:50754 , xlink:href="https://doi.org/10.1002/cplu.201600475"
- Description: Four metalloporphyrin dimers linked by bridging amide-bonded xanthene moieties and that contain either MnIII, CoII, NiII, or CuII metal centers were synthesized. Various spectroscopic, electrochemical, and spectroelectrochemical methods were used to study trends in their properties. Their electronic structure and optical properties were analyzed through a comparison of the electronic absorption and magnetic circular dichroism (MCD) spectral data with the results of time-dependent (TD)-DFT calculations.
- Full Text:
- Date Issued: 2017
- Authors: Li, Minzhi , Zhang, Qian , Xu, Li , Zhu, Weihua , Mack, John , May, Aviwe K , Nyokong, Tebello , Kobayashi, Nagao , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239676 , vital:50754 , xlink:href="https://doi.org/10.1002/cplu.201600475"
- Description: Four metalloporphyrin dimers linked by bridging amide-bonded xanthene moieties and that contain either MnIII, CoII, NiII, or CuII metal centers were synthesized. Various spectroscopic, electrochemical, and spectroelectrochemical methods were used to study trends in their properties. Their electronic structure and optical properties were analyzed through a comparison of the electronic absorption and magnetic circular dichroism (MCD) spectral data with the results of time-dependent (TD)-DFT calculations.
- Full Text:
- Date Issued: 2017
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
Forest degradation and invasive species synergistically impact Mimusops andongensis (Sapotaceae) in Lama Forest Reserve, Benin
- Sinasson, Gisèle K, Shackleton, Charlie M, Glèlè Kakaï, Romain L, Sinsin, Brice
- Authors: Sinasson, Gisèle K , Shackleton, Charlie M , Glèlè Kakaï, Romain L , Sinsin, Brice
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182038 , vital:43792 , xlink:href="https://doi.org/10.1111/btp.12370"
- Description: Harvesting of Non-Timber Forest Products (NTFPs) can threaten target species, especially those with limited distribution and density. Exploited species also face threats from habitat fragmentation, fire, and invasive species. We assessed the impact of human disturbances and invasive species on the population of a key multipurpose NTFP species, Mimusops andongensis, in Lama Forest reserve (Benin). The densities of adult trees and regenerative stems decreased with increasing degradation. Mimusops andongensis contributed less to total tree density with increasing human disturbance. There were significantly fewer M. andongensis recruits with increasing cover of invasive Chromolaena odorata. Smaller diameter individuals predominated in non-degraded and moderately degraded sites while in degraded sites, the structure showed a negative exponential trend with the density of small diameter individuals being less than two trees/ha. Larger individuals were also rare in degraded sites. The low density of both mature trees and seedlings in degraded sites may undermine the long-term viability of M. andongensis, despite existing protection against NTFP harvesting and other anthropogenic pressures. Management should emphasize facilitating recruitment subsidies and limiting the presence of C. odorata.
- Full Text:
- Date Issued: 2017
- Authors: Sinasson, Gisèle K , Shackleton, Charlie M , Glèlè Kakaï, Romain L , Sinsin, Brice
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182038 , vital:43792 , xlink:href="https://doi.org/10.1111/btp.12370"
- Description: Harvesting of Non-Timber Forest Products (NTFPs) can threaten target species, especially those with limited distribution and density. Exploited species also face threats from habitat fragmentation, fire, and invasive species. We assessed the impact of human disturbances and invasive species on the population of a key multipurpose NTFP species, Mimusops andongensis, in Lama Forest reserve (Benin). The densities of adult trees and regenerative stems decreased with increasing degradation. Mimusops andongensis contributed less to total tree density with increasing human disturbance. There were significantly fewer M. andongensis recruits with increasing cover of invasive Chromolaena odorata. Smaller diameter individuals predominated in non-degraded and moderately degraded sites while in degraded sites, the structure showed a negative exponential trend with the density of small diameter individuals being less than two trees/ha. Larger individuals were also rare in degraded sites. The low density of both mature trees and seedlings in degraded sites may undermine the long-term viability of M. andongensis, despite existing protection against NTFP harvesting and other anthropogenic pressures. Management should emphasize facilitating recruitment subsidies and limiting the presence of C. odorata.
- Full Text:
- Date Issued: 2017
Gender, dialogue and discursive psychology: A pilot sexuality intervention with South African high-school learners
- Jearey-Graham, Nicola, Macleod, Catriona I
- Authors: Jearey-Graham, Nicola , Macleod, Catriona I
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/444326 , vital:74219 , xlink:href="https://doi.org/10.1080/14681811.2017.1320983"
- Description: Good-quality sexuality education can be effective in reducing sexual health risks, but may also be disconnected from the lived realities of learners’ lives and reinforce gendered stereotypes. In line with the trend towards ‘empowerment’ in and through sexuality education, we implemented a pilot sexuality intervention with Grade 10 participants following a rigorous consultation process. Nine weekly group dialogues were held with 11 participants, with 2 follow-up sessions the next year. Freirian principles of critical consciousness and dialogical pedagogy, infused with discursive psychological understandings, were used to foreground gendered/sexual norms and to provide recognition for participants in a variety of gendered and sexual subject positions. Sessions were recorded, the facilitator kept a diary, and participants were asked to evaluate the intervention. The dialogical format of the group generated curiosity and engagement, and some participants took up a ‘responsible’ sexual subject position in a reflexive manner. A partial normalisation of some ‘hidden’ aspects of sex was enabled, and critical consciousness around some gendered inequities was promoted. We argue, first, that it is not so much sexuality education that young people need, but sexuality dialogues, and second, that a discursive psychology framework provides a nuanced and fruitful dimension to Freirean inspired ‘empowerment’ sexuality interventions.
- Full Text:
- Date Issued: 2017
- Authors: Jearey-Graham, Nicola , Macleod, Catriona I
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/444326 , vital:74219 , xlink:href="https://doi.org/10.1080/14681811.2017.1320983"
- Description: Good-quality sexuality education can be effective in reducing sexual health risks, but may also be disconnected from the lived realities of learners’ lives and reinforce gendered stereotypes. In line with the trend towards ‘empowerment’ in and through sexuality education, we implemented a pilot sexuality intervention with Grade 10 participants following a rigorous consultation process. Nine weekly group dialogues were held with 11 participants, with 2 follow-up sessions the next year. Freirian principles of critical consciousness and dialogical pedagogy, infused with discursive psychological understandings, were used to foreground gendered/sexual norms and to provide recognition for participants in a variety of gendered and sexual subject positions. Sessions were recorded, the facilitator kept a diary, and participants were asked to evaluate the intervention. The dialogical format of the group generated curiosity and engagement, and some participants took up a ‘responsible’ sexual subject position in a reflexive manner. A partial normalisation of some ‘hidden’ aspects of sex was enabled, and critical consciousness around some gendered inequities was promoted. We argue, first, that it is not so much sexuality education that young people need, but sexuality dialogues, and second, that a discursive psychology framework provides a nuanced and fruitful dimension to Freirean inspired ‘empowerment’ sexuality interventions.
- Full Text:
- Date Issued: 2017
Genetic matching of invasive populations of the African tulip tree, Spathodea campanulata Beauv.(Bignoniaceae), to their native distribution: Maximising the likelihood of selecting host-compatible biological control agents
- Sutton, Guy F, Paterson, Iain D, Paynter, Quentin
- Authors: Sutton, Guy F , Paterson, Iain D , Paynter, Quentin
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/405797 , vital:70207 , xlink:href="https://doi.org/10.1016/j.biocontrol.2017.08.015"
- Description: Spathodea campanulata Beauv (Bignoniaceae) has become a highly damaging environmental and agricultural weed in the Pacific Islands. It has been targeted for biological control due to the costly and inefficient nature of physical and chemical control methods. Determining the origin of weed populations has been increasingly recognised as an important component of successful biological control programmes, and may be important for the biological control of S. campanulata due to the high degree of morphological variability within the species, as well as the broad native distribution. Genetic matching, using inter-simple sequence repeats (ISSR’s), and morphological data found support for invasive Pacific Island S. campanulata plants originating from West Africa. Pacific and West African plants were genetically most similar, and were differentiated from native plants from East/Central Africa by PCA and Bayesian-clustering (STRUCTURE) analyses. Genetic data was corroborated by morphological data which showed that West African and Pacific Islands plants had more sparsely pubescent leaves compared to plants from East/Central Africa. Populations in South Africa, where the plant is introduced but not problematic, originated from a different source population than those in the Pacific Islands, probably in East/Central Africa. A greater sampling effort is required before the origin of the South African populations can be determined with certainty. Herbivores and pathogens for the Pacific Islands should be collected from West Africa as they are more likely to be compatible with S. campanulata plants in this region.
- Full Text:
- Date Issued: 2017
- Authors: Sutton, Guy F , Paterson, Iain D , Paynter, Quentin
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/405797 , vital:70207 , xlink:href="https://doi.org/10.1016/j.biocontrol.2017.08.015"
- Description: Spathodea campanulata Beauv (Bignoniaceae) has become a highly damaging environmental and agricultural weed in the Pacific Islands. It has been targeted for biological control due to the costly and inefficient nature of physical and chemical control methods. Determining the origin of weed populations has been increasingly recognised as an important component of successful biological control programmes, and may be important for the biological control of S. campanulata due to the high degree of morphological variability within the species, as well as the broad native distribution. Genetic matching, using inter-simple sequence repeats (ISSR’s), and morphological data found support for invasive Pacific Island S. campanulata plants originating from West Africa. Pacific and West African plants were genetically most similar, and were differentiated from native plants from East/Central Africa by PCA and Bayesian-clustering (STRUCTURE) analyses. Genetic data was corroborated by morphological data which showed that West African and Pacific Islands plants had more sparsely pubescent leaves compared to plants from East/Central Africa. Populations in South Africa, where the plant is introduced but not problematic, originated from a different source population than those in the Pacific Islands, probably in East/Central Africa. A greater sampling effort is required before the origin of the South African populations can be determined with certainty. Herbivores and pathogens for the Pacific Islands should be collected from West Africa as they are more likely to be compatible with S. campanulata plants in this region.
- Full Text:
- Date Issued: 2017
Gill Memorial Medal Address 2014 Reviewing the Red Bishop: the bird that introduced me to ornithology
- Authors: Craig, Adrian J F K
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/449401 , vital:74818 , https://www.tandfonline.com/doi/pdf/10.2989/00306525.2017.1302754
- Description: Euplectes (Craig 1992). Body mass, high at the start of the breeding season and then declining, increases again during this post-nuptial moult (Craig 1978). An initial analysis of the timing of moult estimated the duration of wing-moult at 110 d on the basis of birds recaptured during moult (Craig and Manson 1979a). Later, these data were reanalysed using new mathematical methods (Craig et al. 2001), which yielded a shorter estimate of 89 d for completion of wing-moult. Moult data from different regions of southern Africa, with samples of> 50 birds, showed striking differences with estimates of the duration of wing-moult ranging from 62 to 114 d (Oschadleus and Underhill 2006; Craig et al. 2010). However, the earlier conclusion that the start of moult in Zimbabwe was significantly later than in KwaZulu-Natal (Craig and Manson 1979a) was not supported when a larger sample of birds from the summer rainfall region was examined (Craig et al. 2010). Nine captive male Red Bishops kept under constant conditions of 14 h light: 10 h dark continued normal cycles of wing-moult, and showed cycles of testis enlargement and regression, but retained either partial or full nuptial plumage over a two-year period (Craig 1985). This suggests that circannual rhythms may play some role in the timing of moult, but further experimental investigations are required to confirm this idea.
- Full Text:
- Date Issued: 2017
- Authors: Craig, Adrian J F K
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/449401 , vital:74818 , https://www.tandfonline.com/doi/pdf/10.2989/00306525.2017.1302754
- Description: Euplectes (Craig 1992). Body mass, high at the start of the breeding season and then declining, increases again during this post-nuptial moult (Craig 1978). An initial analysis of the timing of moult estimated the duration of wing-moult at 110 d on the basis of birds recaptured during moult (Craig and Manson 1979a). Later, these data were reanalysed using new mathematical methods (Craig et al. 2001), which yielded a shorter estimate of 89 d for completion of wing-moult. Moult data from different regions of southern Africa, with samples of> 50 birds, showed striking differences with estimates of the duration of wing-moult ranging from 62 to 114 d (Oschadleus and Underhill 2006; Craig et al. 2010). However, the earlier conclusion that the start of moult in Zimbabwe was significantly later than in KwaZulu-Natal (Craig and Manson 1979a) was not supported when a larger sample of birds from the summer rainfall region was examined (Craig et al. 2010). Nine captive male Red Bishops kept under constant conditions of 14 h light: 10 h dark continued normal cycles of wing-moult, and showed cycles of testis enlargement and regression, but retained either partial or full nuptial plumage over a two-year period (Craig 1985). This suggests that circannual rhythms may play some role in the timing of moult, but further experimental investigations are required to confirm this idea.
- Full Text:
- Date Issued: 2017
Graphene quantum dot-phthalocyanine polystyrene conjugate embedded in asymmetric polymer membranes for photocatalytic oxidation of 4-chlorophenol
- Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189189 , vital:44825 , xlink:href="https://doi.org/10.1080/00958972.2017.1400664"
- Description: The feasibility of using π–π stacking as a means of fixing unsubstituted Zn phthalocyanine (ZnPc) to a support prior to formation of photoactive polymer asymmetric membranes was explored. Stable ZnPc–graphene quantum dot-polystyrene conjugates (6.15 μmol/g ZnPc loading) were synthesized and embedded in polystyrene membranes which proved to be photoactive with a singlet oxygen quantum yield of 0.43 in ethanol and 0.37 in water. The membranes also proved to be active in the photocatalytic oxidation of 4-chlorophenol in water where the reaction followed second-order kinetics. At 3.24 × 10−4 mol L−1, the photo-oxidation of 4-chlorophenol was observed with a kobs of 35.9 L mol−1 min−1 and a half-life of 86 min.
- Full Text:
- Date Issued: 2017
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189189 , vital:44825 , xlink:href="https://doi.org/10.1080/00958972.2017.1400664"
- Description: The feasibility of using π–π stacking as a means of fixing unsubstituted Zn phthalocyanine (ZnPc) to a support prior to formation of photoactive polymer asymmetric membranes was explored. Stable ZnPc–graphene quantum dot-polystyrene conjugates (6.15 μmol/g ZnPc loading) were synthesized and embedded in polystyrene membranes which proved to be photoactive with a singlet oxygen quantum yield of 0.43 in ethanol and 0.37 in water. The membranes also proved to be active in the photocatalytic oxidation of 4-chlorophenol in water where the reaction followed second-order kinetics. At 3.24 × 10−4 mol L−1, the photo-oxidation of 4-chlorophenol was observed with a kobs of 35.9 L mol−1 min−1 and a half-life of 86 min.
- 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
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 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
Halogen substituted A2B type Co (III) triarylcorroles
- Niu, Yingjie, Li, Minzhi, Zhang, Qianchong, Zhu, Weihua, Mack, John, Fomo, Gertrude, Nyokong, Tebello, Liang, Xu
- Authors: Niu, Yingjie , Li, Minzhi , Zhang, Qianchong , 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/10962/233048 , vital:50051 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.02.049"
- Description: Seven low symmetry A2B type Co(III)triarylcorroles with electron withdrawing meso-aryl substituents 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 trends predicted in a series of DFT and TD-DFT calculations. The results demonstrate that Co(III)corroles are highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, there is a marked enhancement in their homogenous catalytic ability when halogen atoms are introduced at the B position, which demonstrates that facile modifying the meso-aryl rings is a effective strategy for developing new HER catalysts. The electrochemical results demonstrate that an unusual two step modulation of HER reactions can be achieved by using singly and doubly electrochemical reduced cobalt triarylcorroles anions.
- Full Text:
- Date Issued: 2017
- Authors: Niu, Yingjie , Li, Minzhi , Zhang, Qianchong , 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/10962/233048 , vital:50051 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.02.049"
- Description: Seven low symmetry A2B type Co(III)triarylcorroles with electron withdrawing meso-aryl substituents 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 trends predicted in a series of DFT and TD-DFT calculations. The results demonstrate that Co(III)corroles are highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, there is a marked enhancement in their homogenous catalytic ability when halogen atoms are introduced at the B position, which demonstrates that facile modifying the meso-aryl rings is a effective strategy for developing new HER catalysts. The electrochemical results demonstrate that an unusual two step modulation of HER reactions can be achieved by using singly and doubly electrochemical reduced cobalt triarylcorroles anions.
- 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
How compatible are urban livestock and urban green spaces and trees?: An assessment in a medium-sized South African town
- Shackleton, Charlie M, Guild, Jenny, Bromham, B, Impey, S, Jarrett, Mitchell, Ngubane, S, Steijl, K
- Authors: Shackleton, Charlie M , Guild, Jenny , Bromham, B , Impey, S , Jarrett, Mitchell , Ngubane, S , Steijl, K
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181048 , vital:43694 , xlink:href="https://doi.org/10.1080/19463138.2017.1314968"
- Description: Urban green spaces and trees provide multiple benefits to urban residents and the sustainability of cities. A poorly examined benefit is the provision of fodder to urban livestock. However, the presence and activities of livestock may be incompatible with other uses, although this has been little studied. We examined the impacts of livestock on trees and parks along a gradient of declining livestock density, complemented with a tree planting experiment to monitor damage. Neighbouring residents and park managers were interviewed regarding their perceptions of damage caused by livestock. The negative impacts on soil compaction, tree damage and death increased with increasing livestock densities. Thorny tree species were damaged significantly less (13 %) than non-thorny species (77 %), as were protected trees (25 %) relative to unprotected ones (65 %). There was more tree damage in public green spaces (PUGS) (54 %) than control sites (38 %). The majority of local residents felt that livestock should not be allowed in formal PUGS, and most urban park managers regarded livestock damage as a strong disincentive to plant trees. These results show the need for management of the trade-offs caused by livestock and greater appreciation of livestock as agents shaping aspects of PUGS.
- Full Text:
- Date Issued: 2017
- Authors: Shackleton, Charlie M , Guild, Jenny , Bromham, B , Impey, S , Jarrett, Mitchell , Ngubane, S , Steijl, K
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181048 , vital:43694 , xlink:href="https://doi.org/10.1080/19463138.2017.1314968"
- Description: Urban green spaces and trees provide multiple benefits to urban residents and the sustainability of cities. A poorly examined benefit is the provision of fodder to urban livestock. However, the presence and activities of livestock may be incompatible with other uses, although this has been little studied. We examined the impacts of livestock on trees and parks along a gradient of declining livestock density, complemented with a tree planting experiment to monitor damage. Neighbouring residents and park managers were interviewed regarding their perceptions of damage caused by livestock. The negative impacts on soil compaction, tree damage and death increased with increasing livestock densities. Thorny tree species were damaged significantly less (13 %) than non-thorny species (77 %), as were protected trees (25 %) relative to unprotected ones (65 %). There was more tree damage in public green spaces (PUGS) (54 %) than control sites (38 %). The majority of local residents felt that livestock should not be allowed in formal PUGS, and most urban park managers regarded livestock damage as a strong disincentive to plant trees. These results show the need for management of the trade-offs caused by livestock and greater appreciation of livestock as agents shaping aspects of PUGS.
- Full Text:
- Date Issued: 2017