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
Eruptive history of the Karoo lava flows and their impact on early Jurassic environmental change:
- Moulin, Maud, Fluteau, Frédéric, Courtillot, Vincent, Marsh, Julian S, Delpech, Guillaume, Quidelleur, Xavier, Gérard, Martine
- Authors: Moulin, Maud , Fluteau, Frédéric , Courtillot, Vincent , Marsh, Julian S , Delpech, Guillaume , Quidelleur, Xavier , Gérard, Martine
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/145098 , vital:38408 , https://doi.org/10.1002/2016JB013354
- Description: This paper reports new paleomagnetic and geochronologic data from a ~1500 m thick composite section belonging to the Drakensberg group, the thickest remnant of the Karoo lavas in Northern Lesotho. Flow‐by‐flow analysis of paleomagnetic directions reveals 21 magnetic directional groups, corresponding to single eruptive events, and 16 individual lava flows. The new age determinations of lava flows range from 180.1 ± 1.4 to 182.8 ± 2.6 Ma. These data, combined with previous results, allow us to propose that the main part of the Drakensberg group and the Karoo intrusive complex dated around 181–183 Ma may have been erupted over a period as short as 250 kyr and may have coincided with the two main phases of extinction in the Early Toarcian. This scenario agrees well with the discontinuous rhythm of environmental and biotic perturbations in the Late Pliensbachian‐Toarcian interval.
- Full Text:
- Date Issued: 2017
- Authors: Moulin, Maud , Fluteau, Frédéric , Courtillot, Vincent , Marsh, Julian S , Delpech, Guillaume , Quidelleur, Xavier , Gérard, Martine
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/145098 , vital:38408 , https://doi.org/10.1002/2016JB013354
- Description: This paper reports new paleomagnetic and geochronologic data from a ~1500 m thick composite section belonging to the Drakensberg group, the thickest remnant of the Karoo lavas in Northern Lesotho. Flow‐by‐flow analysis of paleomagnetic directions reveals 21 magnetic directional groups, corresponding to single eruptive events, and 16 individual lava flows. The new age determinations of lava flows range from 180.1 ± 1.4 to 182.8 ± 2.6 Ma. These data, combined with previous results, allow us to propose that the main part of the Drakensberg group and the Karoo intrusive complex dated around 181–183 Ma may have been erupted over a period as short as 250 kyr and may have coincided with the two main phases of extinction in the Early Toarcian. This scenario agrees well with the discontinuous rhythm of environmental and biotic perturbations in the Late Pliensbachian‐Toarcian interval.
- Full Text:
- Date Issued: 2017
Estimating δ15N fractionation and adjusting the lipid correction equation using Southern African freshwater fishes
- Taylor, Geraldine C, Hill, Jaclyn M, Jackson, Michelle C, Peel, Richard A, Weyl, Olaf L F
- Authors: Taylor, Geraldine C , Hill, Jaclyn M , Jackson, Michelle C , Peel, Richard A , Weyl, Olaf L F
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/69124 , vital:29392 , https://0-doi.org.wam.seals.ac.za/10.1371/journal.pone.0178047
- Description: Stable isotope analysis is an important tool for characterising food web structure; however, interpretation of isotope data can often be flawed. For instance, lipid normalisation and trophic fractionation values are often assumed to be constant, but can vary considerably between ecosystems, species and tissues. Here, previously determined lipid normalisation equations and trophic fractionation values were re-evaluated using freshwater fish species from three rivers in the Upper Zambezian floodplain ecoregion in southern Africa. The parameters commonly used in lipid normalisation equations were not correct for the 18 model species (new D and I parameters were estimated as D = 4.46‰ [95% CI: 2.62, 4.85] and constant I = 0 [95% CI: 0, 0.17]). We suggest that future isotopic analyses on freshwater fishes use our new values if the species under consideration do not have a high lipid content in their white muscle tissue. Nitrogen fractionation values varied between species and river basin; however, the average value closely matched that calculated in previous studies on other species (δ15N fractionation factor of 3.37 ± 1.30 ‰). Here we have highlighted the need to treat stable isotope data correctly in food web studies to avoid misinterpretation of the data.
- Full Text:
- Date Issued: 2017
- Authors: Taylor, Geraldine C , Hill, Jaclyn M , Jackson, Michelle C , Peel, Richard A , Weyl, Olaf L F
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/69124 , vital:29392 , https://0-doi.org.wam.seals.ac.za/10.1371/journal.pone.0178047
- Description: Stable isotope analysis is an important tool for characterising food web structure; however, interpretation of isotope data can often be flawed. For instance, lipid normalisation and trophic fractionation values are often assumed to be constant, but can vary considerably between ecosystems, species and tissues. Here, previously determined lipid normalisation equations and trophic fractionation values were re-evaluated using freshwater fish species from three rivers in the Upper Zambezian floodplain ecoregion in southern Africa. The parameters commonly used in lipid normalisation equations were not correct for the 18 model species (new D and I parameters were estimated as D = 4.46‰ [95% CI: 2.62, 4.85] and constant I = 0 [95% CI: 0, 0.17]). We suggest that future isotopic analyses on freshwater fishes use our new values if the species under consideration do not have a high lipid content in their white muscle tissue. Nitrogen fractionation values varied between species and river basin; however, the average value closely matched that calculated in previous studies on other species (δ15N fractionation factor of 3.37 ± 1.30 ‰). Here we have highlighted the need to treat stable isotope data correctly in food web studies to avoid misinterpretation of the data.
- Full Text:
- Date Issued: 2017
Evaluating the potential of monometallic and bimetallic nanomaterials as horseradish peroxidase mimetics
- Authors: Mvango, Sindisiwe
- Date: 2017
- Subjects: Uncatalogued
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/65134 , vital:28694
- Description: This study presents the synthesis of citrate-capped gold nanoparticles (cit-AuNPs), copper oxide nanoparticles (CuONPs), glutathione-capped gold nanoparticles (GSH-AuNPs), 4- aminothiophenol-capped gold nanoparticles (4-ATP-AuNPs), 4-mercapto benzoic acid- capped gold nanoparticles (4-MBA-AuNPs) and copper oxide gold nanoalloys (CuO-Au nanoalloys). Microscopy and spectroscopy techniques were used to confirm the successful synthesis of these nanoparticles. The synthesized nanoparticles were studied their potential applications as horseradish peroxidase (HPR) enzyme mimetics and for the detection of glucose. The cit-AuNPs and GSH-AuNPs exhibited peroxidase-like activity towards hydrogen peroxide (H2O2) with high Michaelis-Menten (Km) values of 61.5 mM and 30.8 mM, respectively. The other nanoparticles, that is, 4-ATP-AuNPs, CuONPs and CuO-Au nanoalloys gave lower Km values of 4.74 mM, 1.92 mM and 4.05 mM, respectively. The obtained Km values were comparable to those of HRP enzymes which ranged from 0.214 - 3.70 mM with 4-ATP-AuNPs and CuO-Au nanoalloys slightly higher. These values were within the reasonable experimental values of the HRP enzyme. The studies showed that the gold nanoparticles had low adsorptive efficiency towards H2O2 compared to the copper-based nanoparticles (CuONPs and CuO-Au nanoalloys). The CuO-Au nanoalloys also showed the synergistic effect between the gold and copper nanoparticles with extended linear concentration range for the quantification of H2O2. The mechanism of catalysis was confirmed using UV-vis spectroscopy and electron paramagnetic resonance (EPR) in that the generation of reactive oxygen species was observed. The use of 1,3-diphenylisobenzofuran (DPBF) as radical quencher and 5,5- dimethyl-1-pyrroline N-oxide (DMPO) as a radical scavenger confirmed the production of reductive reactive oxygen species using UV-vis and EPR studies. The rate of production of reactive oxygen species in the gold-based nanoparticles was small compared to the copper-based nanoparticles, that is CuONPs and CuO-Au (bimetallic) nanoalloys. The synthesized nanoparticles were further studied their potential use in the colorimetric detection of glucose. The copper-based nanomaterials, CuONPs and CuO-Au nanoalloys, were excellent towards detection of glucose, with a limit of detection (LoD) of 9.34 pM for CuONPs and 6.75 pM for CuO-Au nanoalloys. The linear concentration (LCR) range of CuONPs was 0 to 70 pM and for CuO-Au nanoalloys the LCR was 0.0 - 30 pM. , Thesis (MSc) -- Faculty of Science, Chemistry, 2017
- Full Text:
- Date Issued: 2017
- Authors: Mvango, Sindisiwe
- Date: 2017
- Subjects: Uncatalogued
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/65134 , vital:28694
- Description: This study presents the synthesis of citrate-capped gold nanoparticles (cit-AuNPs), copper oxide nanoparticles (CuONPs), glutathione-capped gold nanoparticles (GSH-AuNPs), 4- aminothiophenol-capped gold nanoparticles (4-ATP-AuNPs), 4-mercapto benzoic acid- capped gold nanoparticles (4-MBA-AuNPs) and copper oxide gold nanoalloys (CuO-Au nanoalloys). Microscopy and spectroscopy techniques were used to confirm the successful synthesis of these nanoparticles. The synthesized nanoparticles were studied their potential applications as horseradish peroxidase (HPR) enzyme mimetics and for the detection of glucose. The cit-AuNPs and GSH-AuNPs exhibited peroxidase-like activity towards hydrogen peroxide (H2O2) with high Michaelis-Menten (Km) values of 61.5 mM and 30.8 mM, respectively. The other nanoparticles, that is, 4-ATP-AuNPs, CuONPs and CuO-Au nanoalloys gave lower Km values of 4.74 mM, 1.92 mM and 4.05 mM, respectively. The obtained Km values were comparable to those of HRP enzymes which ranged from 0.214 - 3.70 mM with 4-ATP-AuNPs and CuO-Au nanoalloys slightly higher. These values were within the reasonable experimental values of the HRP enzyme. The studies showed that the gold nanoparticles had low adsorptive efficiency towards H2O2 compared to the copper-based nanoparticles (CuONPs and CuO-Au nanoalloys). The CuO-Au nanoalloys also showed the synergistic effect between the gold and copper nanoparticles with extended linear concentration range for the quantification of H2O2. The mechanism of catalysis was confirmed using UV-vis spectroscopy and electron paramagnetic resonance (EPR) in that the generation of reactive oxygen species was observed. The use of 1,3-diphenylisobenzofuran (DPBF) as radical quencher and 5,5- dimethyl-1-pyrroline N-oxide (DMPO) as a radical scavenger confirmed the production of reductive reactive oxygen species using UV-vis and EPR studies. The rate of production of reactive oxygen species in the gold-based nanoparticles was small compared to the copper-based nanoparticles, that is CuONPs and CuO-Au (bimetallic) nanoalloys. The synthesized nanoparticles were further studied their potential use in the colorimetric detection of glucose. The copper-based nanomaterials, CuONPs and CuO-Au nanoalloys, were excellent towards detection of glucose, with a limit of detection (LoD) of 9.34 pM for CuONPs and 6.75 pM for CuO-Au nanoalloys. The linear concentration (LCR) range of CuONPs was 0 to 70 pM and for CuO-Au nanoalloys the LCR was 0.0 - 30 pM. , Thesis (MSc) -- Faculty of Science, Chemistry, 2017
- Full Text:
- Date Issued: 2017
Evaluation of the acceptability of ambulatory blood pressure monitoring in a semi-rural, Eastern Cape population
- Authors: Chiwanza, Farisai
- Date: 2017
- Language: English
- Type: text , Thesis , Masters , MPharm
- Identifier: http://hdl.handle.net/10962/59161 , vital:27447
- Description: Expected release date-April 2019
- Full Text:
- Date Issued: 2017
- Authors: Chiwanza, Farisai
- Date: 2017
- Language: English
- Type: text , Thesis , Masters , MPharm
- Identifier: http://hdl.handle.net/10962/59161 , vital:27447
- Description: Expected release date-April 2019
- Full Text:
- Date Issued: 2017
Evidence for rangewide panmixia despite multiple barriers to dispersal in a marine mussel
- Lourenço, Carla R, Nicastro, Katy R, McQuaid, Christopher D, Chefaoui, Rosa M, Assis, Jorge, Taleb, Mohammed Z, Zardi, Gerardo I
- Authors: Lourenço, Carla R , Nicastro, Katy R , McQuaid, Christopher D , Chefaoui, Rosa M , Assis, Jorge , Taleb, Mohammed Z , Zardi, Gerardo I
- Date: 2017
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59952 , vital:27714 , doi:10.1038/s41598-017-10753-9
- Description: Oceanographic features shape the distributional and genetic patterns of marine species by interrupting or promoting connections among populations. Although general patterns commonly arise, distributional ranges and genetic structure are species-specific and do not always comply with the expected trends. By applying a multimarker genetic approach combined with Lagrangian particle simulations (LPS) we tested the hypothesis that oceanographic features along northeastern Atlantic and Mediterranean shores influence dispersal potential and genetic structure of the intertidal mussel Perna perna. Additionally, by performing environmental niche modelling we assessed the potential and realized niche of P. perna along its entire native distributional range and the environmental factors that best explain its realized distribution. Perna perna showed evidence of panmixia across 4,000 km despite several oceanographic breaking points detected by LPS. This is probably the result of a combination of life history traits, continuous habitat availability and stepping-stone dynamics. Moreover, the niche modelling framework depicted minimum sea surface temperatures (SST) as the major factor shaping P. perna distributional range limits along its native areas. Forthcoming warming SST is expected to further change these limits and allow the species to expand its range polewards though this may be accompanied by retreat from warmer areas.
- Full Text:
- Date Issued: 2017
- Authors: Lourenço, Carla R , Nicastro, Katy R , McQuaid, Christopher D , Chefaoui, Rosa M , Assis, Jorge , Taleb, Mohammed Z , Zardi, Gerardo I
- Date: 2017
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59952 , vital:27714 , doi:10.1038/s41598-017-10753-9
- Description: Oceanographic features shape the distributional and genetic patterns of marine species by interrupting or promoting connections among populations. Although general patterns commonly arise, distributional ranges and genetic structure are species-specific and do not always comply with the expected trends. By applying a multimarker genetic approach combined with Lagrangian particle simulations (LPS) we tested the hypothesis that oceanographic features along northeastern Atlantic and Mediterranean shores influence dispersal potential and genetic structure of the intertidal mussel Perna perna. Additionally, by performing environmental niche modelling we assessed the potential and realized niche of P. perna along its entire native distributional range and the environmental factors that best explain its realized distribution. Perna perna showed evidence of panmixia across 4,000 km despite several oceanographic breaking points detected by LPS. This is probably the result of a combination of life history traits, continuous habitat availability and stepping-stone dynamics. Moreover, the niche modelling framework depicted minimum sea surface temperatures (SST) as the major factor shaping P. perna distributional range limits along its native areas. Forthcoming warming SST is expected to further change these limits and allow the species to expand its range polewards though this may be accompanied by retreat from warmer areas.
- Full Text:
- Date Issued: 2017
Evil and the Hero-Villain Binary in Deon Meyer’s Post-Apartheid Crime Thriller, Devil’s Peak:
- Naidu, Samantha, van der Wielen, Karlien
- Authors: Naidu, Samantha , van der Wielen, Karlien
- Date: 2017
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/157991 , vital:40137 , ISBN 9781498533423
- Description: The Functions of Evil Across Disciplinary Contexts explores answers to two important questions about the age-old theme of evil: is there any use in using the concept of evil in cultural, psychological, or other secular evaluations of the world and its productions? Most importantly, if there is, what might these functions be? By looking across several disciplines and analyzing evil as it is referenced across a broad spectrum of phenomena, this work demonstrates the varying ways that we interact with the ethical dilemma as academics, as citizens, and as people. The work draws from authors in different fields—including history, literary and film studies, philosophy, and psychology—and from around the world to provide an analysis of evil in such topics as deeply canonical as Beowulf and Shakespeare to subjects as culturally resonant as Stephen King, Captain America, or the War on Terror. By bringing together this otherwise disparate collection of scholarship, this collection reveals that discussions of evil across disciplines have always been questions of how cultures represent that which they find socially abhorrent. This work thus opens the conversation about evil outside of field-specific limitations, simultaneously demonstrating the assumptions that undergird the manner by which such a conversation proceeds.
- Full Text:
- Date Issued: 2017
- Authors: Naidu, Samantha , van der Wielen, Karlien
- Date: 2017
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/157991 , vital:40137 , ISBN 9781498533423
- Description: The Functions of Evil Across Disciplinary Contexts explores answers to two important questions about the age-old theme of evil: is there any use in using the concept of evil in cultural, psychological, or other secular evaluations of the world and its productions? Most importantly, if there is, what might these functions be? By looking across several disciplines and analyzing evil as it is referenced across a broad spectrum of phenomena, this work demonstrates the varying ways that we interact with the ethical dilemma as academics, as citizens, and as people. The work draws from authors in different fields—including history, literary and film studies, philosophy, and psychology—and from around the world to provide an analysis of evil in such topics as deeply canonical as Beowulf and Shakespeare to subjects as culturally resonant as Stephen King, Captain America, or the War on Terror. By bringing together this otherwise disparate collection of scholarship, this collection reveals that discussions of evil across disciplines have always been questions of how cultures represent that which they find socially abhorrent. This work thus opens the conversation about evil outside of field-specific limitations, simultaneously demonstrating the assumptions that undergird the manner by which such a conversation proceeds.
- Full Text:
- Date Issued: 2017
Examining the nature of learning within an afterschool mathematics club : a case study of four learners
- Pohamba, Penehafo K, Graven, Mellony, Stott, Deborah A, Ashipala, Daniel O
- Authors: Pohamba, Penehafo K , Graven, Mellony , Stott, Deborah A , Ashipala, Daniel O
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/70121 , vital:29623 , http://dx.doi.org/10.5430/irhe.v2n1p21
- Description: This study examined the nature of learning within an afterschool mathematics club established by the South African Numeracy Chair project. This study sought to establish what sort of progress in mathematical learning occurred in a grade 3 afterschool maths club, using assessment instruments associated with the Learning Framework in Number. The study also sought to understand the nature and effects of mentor mediation in the maths club, using Vygotsky’s notion of the Zone of Proximal Development (ZPD) together with the notion and practice of scaffolding. This study was interpretive in nature drawing on qualitative methods with some elements of quantification in relation to learners’ progression. The club consists of 10 learners of mixed ability (5 girls and 5 boys) at a township school in Graham’s town, South Africa. Learners in this case study were selected through purposive sampling. As part of the data collection strategies, the learners were interviewed twice in terms of their numeracy proficiency. The assessment interview results revealed that, in terms of proficiency in early arithmetical learning, all four learners showed progress after spending four months in an afterschool maths club. This study also recommended Wright et al.’s (2006) LFIN framework to be used in assessing learners’ progress in mathematics, as it could inform the refinement of instructional design within the school curriculum and teachers’ education in the Namibian context.
- Full Text:
- Date Issued: 2017
- Authors: Pohamba, Penehafo K , Graven, Mellony , Stott, Deborah A , Ashipala, Daniel O
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/70121 , vital:29623 , http://dx.doi.org/10.5430/irhe.v2n1p21
- Description: This study examined the nature of learning within an afterschool mathematics club established by the South African Numeracy Chair project. This study sought to establish what sort of progress in mathematical learning occurred in a grade 3 afterschool maths club, using assessment instruments associated with the Learning Framework in Number. The study also sought to understand the nature and effects of mentor mediation in the maths club, using Vygotsky’s notion of the Zone of Proximal Development (ZPD) together with the notion and practice of scaffolding. This study was interpretive in nature drawing on qualitative methods with some elements of quantification in relation to learners’ progression. The club consists of 10 learners of mixed ability (5 girls and 5 boys) at a township school in Graham’s town, South Africa. Learners in this case study were selected through purposive sampling. As part of the data collection strategies, the learners were interviewed twice in terms of their numeracy proficiency. The assessment interview results revealed that, in terms of proficiency in early arithmetical learning, all four learners showed progress after spending four months in an afterschool maths club. This study also recommended Wright et al.’s (2006) LFIN framework to be used in assessing learners’ progress in mathematics, as it could inform the refinement of instructional design within the school curriculum and teachers’ education in the Namibian context.
- 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
Extended use of grey water for irrigating home gardens in an arid environment
- Al-Ismaili, Abdulrahim M, Ahmed, Mushtaque, Al-Busaidi, Ahmed, Al-Adawi, Seif, Tandlich, Roman, Al-Amri, Mohammed
- Authors: Al-Ismaili, Abdulrahim M , Ahmed, Mushtaque , Al-Busaidi, Ahmed , Al-Adawi, Seif , Tandlich, Roman , Al-Amri, Mohammed
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76048 , vital:30497 , https://doi.org/10.1007/s11356-017-8963-z
- Description: The use of treated grey water (GW) for home gardens, peri-urban agriculture and landscaping is becoming popular in many water stressed countries such as Oman. This study aims to investigate the treatment efficacy, health and chemical concerns, cost-benefits and maintenance protocol of a GW treatment system as well as the effect of irrigation with GW on crop yield. Therefore, a decentralized homemade GW treatment system was installed in a newly constructed house in Muscat, Oman and studied over a 2-year period. The treated GW was found to be suitable for irrigation as per Omani standards. GW when mixed with kitchen effluent substituted the use of nutrient supplements for plants and did not show any harmful chemical or biological contamination. The capital cost of the system was around US $980, and the annual operating cost was US $78 with annual income and savings from the system being around US $572 indicating a payback period of nearly 2 years. It was found that the system required simple but regular maintenance particularly cleaning of the top layer of the filter. It can be concluded from this study that such a GW system should be technically, economically and environmentally feasible in Oman. Also, wider acceptance by the general public to the idea of GW reuse will help in mitigating the water shortage problem of the country to some extent.
- Full Text:
- Date Issued: 2017
- Authors: Al-Ismaili, Abdulrahim M , Ahmed, Mushtaque , Al-Busaidi, Ahmed , Al-Adawi, Seif , Tandlich, Roman , Al-Amri, Mohammed
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76048 , vital:30497 , https://doi.org/10.1007/s11356-017-8963-z
- Description: The use of treated grey water (GW) for home gardens, peri-urban agriculture and landscaping is becoming popular in many water stressed countries such as Oman. This study aims to investigate the treatment efficacy, health and chemical concerns, cost-benefits and maintenance protocol of a GW treatment system as well as the effect of irrigation with GW on crop yield. Therefore, a decentralized homemade GW treatment system was installed in a newly constructed house in Muscat, Oman and studied over a 2-year period. The treated GW was found to be suitable for irrigation as per Omani standards. GW when mixed with kitchen effluent substituted the use of nutrient supplements for plants and did not show any harmful chemical or biological contamination. The capital cost of the system was around US $980, and the annual operating cost was US $78 with annual income and savings from the system being around US $572 indicating a payback period of nearly 2 years. It was found that the system required simple but regular maintenance particularly cleaning of the top layer of the filter. It can be concluded from this study that such a GW system should be technically, economically and environmentally feasible in Oman. Also, wider acceptance by the general public to the idea of GW reuse will help in mitigating the water shortage problem of the country to some extent.
- Full Text:
- Date Issued: 2017
Extracellular Hsp90 and TGFP regulate adhesion, migration and anchorage independent growth in a paired colon cancer cell line model
- de la Mare, Jo-Anne, Jurgens, Tamarin, Edkins, Adrienne L
- Authors: de la Mare, Jo-Anne , Jurgens, Tamarin , Edkins, Adrienne L
- Date: 2017
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59920 , vital:27710 , https://doi.org/10.1186/s12885-017-3190-z
- Description: Tumour metastasis remains the major cause of death in cancer patients and, to date, the mechanism and signalling pathways governing this process are not completely understood. The TGF-ß pathway is the most commonly mutated pathway in cancer, however its role in cancer progression is controversial as it can function as both a promoter and a suppressor of metastasis. Although previous studies have suggested a role for the molecular chaperone Hsp90 in regulating the TGF-ß pathway, the level at which this occurs as well as the consequences in terms of colon cancer metastasis are unknown.
- Full Text:
- Date Issued: 2017
- Authors: de la Mare, Jo-Anne , Jurgens, Tamarin , Edkins, Adrienne L
- Date: 2017
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59920 , vital:27710 , https://doi.org/10.1186/s12885-017-3190-z
- Description: Tumour metastasis remains the major cause of death in cancer patients and, to date, the mechanism and signalling pathways governing this process are not completely understood. The TGF-ß pathway is the most commonly mutated pathway in cancer, however its role in cancer progression is controversial as it can function as both a promoter and a suppressor of metastasis. Although previous studies have suggested a role for the molecular chaperone Hsp90 in regulating the TGF-ß pathway, the level at which this occurs as well as the consequences in terms of colon cancer metastasis are unknown.
- 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
Facilitators for and barriers to the implementation of National Tuberculosis Management Guidelines
- Dlwati, Lucretia V, Mavundla, Thandisizwe R, Mbengo, Fungai
- Authors: Dlwati, Lucretia V , Mavundla, Thandisizwe R , Mbengo, Fungai
- Date: 2017
- Subjects: TB management , National Tuberculosis Management Guidelines , Normalization Process Model
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/11260/5569 , vital:44607 , https://doi.org/10.25159/2520-5293/2862
- Description: The South African government developed the National Tuberculosis Management Guidelines (NTBMGs) to provide guidance to professional healthcare workers on the management of people with TB and also those co-infected with HIV. However, little is known about primary healthcare (PHC) nurses perceptions of the implementation of the NTBMGs, despite their critical role in TB management. The purpose of this study was to explore PHC nurses perception of the implementation of the NTBMGs in order to identify factors influencing the implementation of the NTBMGs and to make recommendations to improve the implementation of the NTBMGs. The study was conducted in the Eastern Cape, South Africa. The Normalization Process Model (NPM) was used as a theoretical framework to understand the factors influencing the implementation of the NTBMGs. A qualitative, explorative, descriptive and contextual research design was utilised. Data were collected using individual semi-structured interviews on a purposive sample of PHC nurses working in rural clinics. Data were analysed following a descriptive method of Tesch. The study revealed several facilitators for and barriers to the implementation of the NTBMGs based on the NPM. The facilitators included the PHC nurses satisfaction with the Directly Observed Treatment, Short Course (DOTS) strategy in rendering health services to TB patients, the PHC nurses perception of TB meetings as an appropriate platform for problem-solving, of the NTBMGs to be consistent with TB management, and of job satisfaction in relation to patient improvement. The barriers included poverty, inadequate training, shortage of staff, and a lack of material resources, a proper infection control policy, and space. There is a need for the provision of adequate human, material and infrastructural resources in order to eliminate the barriers to the implementation of the NTBMGs.
- Full Text:
- Date Issued: 2017
- Authors: Dlwati, Lucretia V , Mavundla, Thandisizwe R , Mbengo, Fungai
- Date: 2017
- Subjects: TB management , National Tuberculosis Management Guidelines , Normalization Process Model
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/11260/5569 , vital:44607 , https://doi.org/10.25159/2520-5293/2862
- Description: The South African government developed the National Tuberculosis Management Guidelines (NTBMGs) to provide guidance to professional healthcare workers on the management of people with TB and also those co-infected with HIV. However, little is known about primary healthcare (PHC) nurses perceptions of the implementation of the NTBMGs, despite their critical role in TB management. The purpose of this study was to explore PHC nurses perception of the implementation of the NTBMGs in order to identify factors influencing the implementation of the NTBMGs and to make recommendations to improve the implementation of the NTBMGs. The study was conducted in the Eastern Cape, South Africa. The Normalization Process Model (NPM) was used as a theoretical framework to understand the factors influencing the implementation of the NTBMGs. A qualitative, explorative, descriptive and contextual research design was utilised. Data were collected using individual semi-structured interviews on a purposive sample of PHC nurses working in rural clinics. Data were analysed following a descriptive method of Tesch. The study revealed several facilitators for and barriers to the implementation of the NTBMGs based on the NPM. The facilitators included the PHC nurses satisfaction with the Directly Observed Treatment, Short Course (DOTS) strategy in rendering health services to TB patients, the PHC nurses perception of TB meetings as an appropriate platform for problem-solving, of the NTBMGs to be consistent with TB management, and of job satisfaction in relation to patient improvement. The barriers included poverty, inadequate training, shortage of staff, and a lack of material resources, a proper infection control policy, and space. There is a need for the provision of adequate human, material and infrastructural resources in order to eliminate the barriers to the implementation of the NTBMGs.
- Full Text:
- Date Issued: 2017
Fibronectin is a stress responsive gene regulated by HSF1 in response to geldanamycin
- Dhanani, Karim C H, Samson, William J, Edkins, Adrienne L
- Authors: Dhanani, Karim C H , Samson, William J , Edkins, Adrienne L
- Date: 2017
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59931 , vital:27711 , https://doi:10.1038/s41598-017-18061-y
- Description: Fibronectin is an extracellular matrix glycoprotein with key roles in cell adhesion and migration. Hsp90 binds directly to fibronectin and Hsp90 depletion regulates fibronectin matrix stability. Where inhibition of Hsp90 with a C-terminal inhibitor, novobiocin, reduced the fibronectin matrix, treatment with an N-terminal inhibitor, geldanamycin, increased fibronectin levels. Geldanamycin treatment induced a stress response and a strong dose and time dependent increase in fibronectin mRNA via activation of the fibronectin promoter. Three putative heat shock elements (HSEs) were identified in the fibronectin promoter. Loss of two of these HSEs reduced both basal and geldanamycin-induced promoter activity, as did inhibition of the stress-responsive transcription factor HSF1. Binding of HSF1 to one of the putative HSE was confirmed by ChIP under basal conditions, and occupancy shown to increase with geldanamycin treatment. These data support the hypothesis that fibronectin is stress-responsive and a functional HSF1 target gene. COLA42 and LAMB3 mRNA levels were also increased with geldanamycin indicating that regulation of extracellular matrix (ECM) genes by HSF1 may be a wider phenomenon. Taken together, these data have implications for our understanding of ECM dynamics in stress-related diseases in which HSF1 is activated, and where the clinical application of N-terminal Hsp90 inhibitors is intended.
- Full Text:
- Date Issued: 2017
- Authors: Dhanani, Karim C H , Samson, William J , Edkins, Adrienne L
- Date: 2017
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59931 , vital:27711 , https://doi:10.1038/s41598-017-18061-y
- Description: Fibronectin is an extracellular matrix glycoprotein with key roles in cell adhesion and migration. Hsp90 binds directly to fibronectin and Hsp90 depletion regulates fibronectin matrix stability. Where inhibition of Hsp90 with a C-terminal inhibitor, novobiocin, reduced the fibronectin matrix, treatment with an N-terminal inhibitor, geldanamycin, increased fibronectin levels. Geldanamycin treatment induced a stress response and a strong dose and time dependent increase in fibronectin mRNA via activation of the fibronectin promoter. Three putative heat shock elements (HSEs) were identified in the fibronectin promoter. Loss of two of these HSEs reduced both basal and geldanamycin-induced promoter activity, as did inhibition of the stress-responsive transcription factor HSF1. Binding of HSF1 to one of the putative HSE was confirmed by ChIP under basal conditions, and occupancy shown to increase with geldanamycin treatment. These data support the hypothesis that fibronectin is stress-responsive and a functional HSF1 target gene. COLA42 and LAMB3 mRNA levels were also increased with geldanamycin indicating that regulation of extracellular matrix (ECM) genes by HSF1 may be a wider phenomenon. Taken together, these data have implications for our understanding of ECM dynamics in stress-related diseases in which HSF1 is activated, and where the clinical application of N-terminal Hsp90 inhibitors is intended.
- Full Text:
- Date Issued: 2017
Figuring maternity: Christine Dixie's Parturient Prospects
- Authors: Schmahmann, Brenda
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/147748 , vital:38667 , https://doi.org/10.1080/00043389.2007.11877068
- Description: The Interior, Birthing Tray and Parturition are three sub-sections of a project entitled Parturient Prospects that artist Christine Dixie began in 2005, when she was pregnant with her second child, and completed by the end of 2006. In Parturient Prospects, the author reveals, Dixie situates her experiences against Western discourses, especially images from early modern Europe. Focusing on the ways in which visual representations construct woman as ‘other’, Dixie invokes reference to not only representations of birth and maternity but also religious, medical and geographical images.
- Full Text:
- Date Issued: 2017
- Authors: Schmahmann, Brenda
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/147748 , vital:38667 , https://doi.org/10.1080/00043389.2007.11877068
- Description: The Interior, Birthing Tray and Parturition are three sub-sections of a project entitled Parturient Prospects that artist Christine Dixie began in 2005, when she was pregnant with her second child, and completed by the end of 2006. In Parturient Prospects, the author reveals, Dixie situates her experiences against Western discourses, especially images from early modern Europe. Focusing on the ways in which visual representations construct woman as ‘other’, Dixie invokes reference to not only representations of birth and maternity but also religious, medical and geographical images.
- 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
Forensic entomotoxicology revisited: towards professional standardisation of study designs
- da Silva, Erica I T, Wilhelmi, Brendan S, Villet, Martin H
- Authors: da Silva, Erica I T , Wilhelmi, Brendan S , Villet, Martin H
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/140819 , vital:37921 , DOI: 10.1007/s00414-017-1603-9
- Description: Forensic entomotoxicology is the use of insects as evidence of whether a toxicant is present in an environment such as a corpse, river or landscape. The earliest overtly forensic study was published in 1977, and since then, at least 63 papers have been published, most of them focused on the detection of toxicants in insects or on effects of toxicants on diverse insect indicator taxa. A comprehensive review of the published literature revealed various inconsistencies between studies that could be addressed by introducing standard protocols for such studies. These protocols could include selecting widespread and common model organisms (such as Lucilia sericata, Calliphora vicina, Chrysomya megacephala and Dermestes maculatus) and model toxicants (e.g. morphine and amitriptyline) to build up comparative databases; developing a standard matrix for use as a feeding substrate; setting guidelines for statistically adequate sample sizes; and deploying more sophisticated analytical methods from the general field of toxicology.
- Full Text:
- Date Issued: 2017
- Authors: da Silva, Erica I T , Wilhelmi, Brendan S , Villet, Martin H
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/140819 , vital:37921 , DOI: 10.1007/s00414-017-1603-9
- Description: Forensic entomotoxicology is the use of insects as evidence of whether a toxicant is present in an environment such as a corpse, river or landscape. The earliest overtly forensic study was published in 1977, and since then, at least 63 papers have been published, most of them focused on the detection of toxicants in insects or on effects of toxicants on diverse insect indicator taxa. A comprehensive review of the published literature revealed various inconsistencies between studies that could be addressed by introducing standard protocols for such studies. These protocols could include selecting widespread and common model organisms (such as Lucilia sericata, Calliphora vicina, Chrysomya megacephala and Dermestes maculatus) and model toxicants (e.g. morphine and amitriptyline) to build up comparative databases; developing a standard matrix for use as a feeding substrate; setting guidelines for statistically adequate sample sizes; and deploying more sophisticated analytical methods from the general field of toxicology.
- Full Text:
- Date Issued: 2017