Differentiations and intersections: a corpus-assisted discourse study of gender representations in the British press before, during and after the London Olympics 2012
- Jaworska, Sylvia, Hunt, Sally
- Authors: Jaworska, Sylvia , Hunt, Sally
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/139205 , vital:37714 , DOI 10.1558/genl.28858
- Description: This study examines the impact of a global sports event on gender representations in media reporting. Whereas previous research on gender, sport and media has been mainly concerned with sports events in the North American or Australian context, this study investigates the British media reporting before, during and after the London Olympics 2012. Our study follows the approach of Corpus-Assisted Discourse Studies (CADS) and uses both quantitative and qualitative research procedures. The results reveal more balanced gender representations during the London Olympics in that the ‘regular’ biased associations were supressed in favour of positive references to female achievements. However, little carry-though of the ‘gains’ was noted. Also, this study shows that the positive associations intersected with national sentiments and were used to celebrate the nation-state. At the same time, some subtle resistance was observed to accepting as ‘truly’ British the non-white athletes and those not born in Britain.
- Full Text:
- Date Issued: 2017
- Authors: Jaworska, Sylvia , Hunt, Sally
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/139205 , vital:37714 , DOI 10.1558/genl.28858
- Description: This study examines the impact of a global sports event on gender representations in media reporting. Whereas previous research on gender, sport and media has been mainly concerned with sports events in the North American or Australian context, this study investigates the British media reporting before, during and after the London Olympics 2012. Our study follows the approach of Corpus-Assisted Discourse Studies (CADS) and uses both quantitative and qualitative research procedures. The results reveal more balanced gender representations during the London Olympics in that the ‘regular’ biased associations were supressed in favour of positive references to female achievements. However, little carry-though of the ‘gains’ was noted. Also, this study shows that the positive associations intersected with national sentiments and were used to celebrate the nation-state. At the same time, some subtle resistance was observed to accepting as ‘truly’ British the non-white athletes and those not born in Britain.
- Full Text:
- Date Issued: 2017
Disclaiming/denigrating/dodging: white South African academics’ everyday racetalk
- Vincent, Louise, Idahosa, Grace E, Msomi, Zuziwe
- Authors: Vincent, Louise , Idahosa, Grace E , Msomi, Zuziwe
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/141900 , vital:38014 , DOI: 10.1080/14725843.2017.1292119
- Description: The call for the ‘transformation’ of higher education in South Africa is one instance of a wider effort, since the country’s first democratic election in 1994, to surmount an apartheid and colonial legacy of institutionalised racism. In 2015 and 2016 nationwide protests led to universities being shut down as students and staff expressed frustration institutions that continue to be experienced as racist and ‘untransformed’. In this study we report on interviews conducted with senior white academics at one South African university shortly before these protests began. Given that our participants are people of influence in their respective university departments, we asked, in in-depth open-ended interviews, what contribution they saw themselves making to ‘transformation’. We argue that the talk of these participants could be described as what authors in the field call 'racetalk', Talk is understood here as a form of social practice, the analysis of which helps us to understand how racism is reproduced in mundane ways which, taken together, account for the persistence of pervasive institutionalised racism in South African higher education that appears impervious to policy and regime change.
- Full Text:
- Date Issued: 2017
- Authors: Vincent, Louise , Idahosa, Grace E , Msomi, Zuziwe
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/141900 , vital:38014 , DOI: 10.1080/14725843.2017.1292119
- Description: The call for the ‘transformation’ of higher education in South Africa is one instance of a wider effort, since the country’s first democratic election in 1994, to surmount an apartheid and colonial legacy of institutionalised racism. In 2015 and 2016 nationwide protests led to universities being shut down as students and staff expressed frustration institutions that continue to be experienced as racist and ‘untransformed’. In this study we report on interviews conducted with senior white academics at one South African university shortly before these protests began. Given that our participants are people of influence in their respective university departments, we asked, in in-depth open-ended interviews, what contribution they saw themselves making to ‘transformation’. We argue that the talk of these participants could be described as what authors in the field call 'racetalk', Talk is understood here as a form of social practice, the analysis of which helps us to understand how racism is reproduced in mundane ways which, taken together, account for the persistence of pervasive institutionalised racism in South African higher education that appears impervious to policy and regime change.
- Full Text:
- Date Issued: 2017
Distributed leadership in South Africa
- Authors: Grant, Carolyn
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281024 , vital:55684 , xlink:href="https://doi.org/10.1080/13632434.2017.1360856"
- Description: Distributed leadership, while an established concept in the international literature on education leadership, is slowly gaining prominence in post-apartheid South Africa. This is primarily due to its normative and representational appeal. However, of concern is that the concept has become a catch-all phrase to describe any form of devolved or shared leadership and is being espoused as ‘the answer’ to the country’s educational leadership woes. Drawing on a South African publications-based doctoral study of distributed teacher leadership (Grant 2010. “Distributed Teacher Leadership: Troubling the Terrain.” Unpublished PhD diss., University of KwaZulu-Natal, Pietermaritzburg) for its evidence, this article argues for a theoretically robust form of distributed leadership conceptualised as socio-cultural practice and framed as a product of the joint interactions of school leaders, followers and aspects of their situation (Gronn 2000. “Distributed Properties: A New Architecture for Leadership.” Educational Management and Administration 28 (3): 317–338; Spillane, Halverson and Diamond 2004. “Towards a Theory of Leadership Practice: A Distributed Perspective.” Journal of Curriculum Studies 36 (1): 3–34; Spillane 2006. Distributed Leadership. San Francisco: Jossey-Bass). It endorses a sequential distributed leadership framing for the South African context and calls for further empirical studies which interrogate the complex practices of distributed school leadership. For without this theoretically robust work, the article argues, distributed leadership is likely to be relegated to the large pile of redundant leadership theories and become a passing fad.
- Full Text:
- Date Issued: 2017
- Authors: Grant, Carolyn
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281024 , vital:55684 , xlink:href="https://doi.org/10.1080/13632434.2017.1360856"
- Description: Distributed leadership, while an established concept in the international literature on education leadership, is slowly gaining prominence in post-apartheid South Africa. This is primarily due to its normative and representational appeal. However, of concern is that the concept has become a catch-all phrase to describe any form of devolved or shared leadership and is being espoused as ‘the answer’ to the country’s educational leadership woes. Drawing on a South African publications-based doctoral study of distributed teacher leadership (Grant 2010. “Distributed Teacher Leadership: Troubling the Terrain.” Unpublished PhD diss., University of KwaZulu-Natal, Pietermaritzburg) for its evidence, this article argues for a theoretically robust form of distributed leadership conceptualised as socio-cultural practice and framed as a product of the joint interactions of school leaders, followers and aspects of their situation (Gronn 2000. “Distributed Properties: A New Architecture for Leadership.” Educational Management and Administration 28 (3): 317–338; Spillane, Halverson and Diamond 2004. “Towards a Theory of Leadership Practice: A Distributed Perspective.” Journal of Curriculum Studies 36 (1): 3–34; Spillane 2006. Distributed Leadership. San Francisco: Jossey-Bass). It endorses a sequential distributed leadership framing for the South African context and calls for further empirical studies which interrogate the complex practices of distributed school leadership. For without this theoretically robust work, the article argues, distributed leadership is likely to be relegated to the large pile of redundant leadership theories and become a passing fad.
- Full Text:
- Date Issued: 2017
Dose response and kinetic analysis of thermoluminescence of Li–Zn fluoroborate glass
- Thomas, Sunil, Chithambo, Makaiko L
- Authors: Thomas, Sunil , Chithambo, Makaiko L
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/116164 , vital:34326 , https://doi.org/10.1080/10420150.2017.1313844
- Description: The intention of this study is to explore the thermoluminescence properties of beta-irradiated Li–Zn fluoroborate glass. The glow-curve corresponding to 10 Gy shows two peaks when measured at 1°C/s. The dose response of the glass to beta irradiation was investigated. The trapping level parameters such as activation energy, frequency factor and order of kinetics associated with the observed glow-peak were determined using different methods. The thermoluminescence is affected by thermal quenching. A possible mechanism for the thermoluminescence is described.
- Full Text:
- Date Issued: 2017
- Authors: Thomas, Sunil , Chithambo, Makaiko L
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/116164 , vital:34326 , https://doi.org/10.1080/10420150.2017.1313844
- Description: The intention of this study is to explore the thermoluminescence properties of beta-irradiated Li–Zn fluoroborate glass. The glow-curve corresponding to 10 Gy shows two peaks when measured at 1°C/s. The dose response of the glass to beta irradiation was investigated. The trapping level parameters such as activation energy, frequency factor and order of kinetics associated with the observed glow-peak were determined using different methods. The thermoluminescence is affected by thermal quenching. A possible mechanism for the thermoluminescence is described.
- Full Text:
- Date Issued: 2017
Ecosystem-scale impacts of non-timber forest product harvesting: Effects on soil nutrients
- Ruwanza, Sheunesu, Shackleton, Charlie M
- Authors: Ruwanza, Sheunesu , Shackleton, Charlie M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180099 , vital:43309 , xlink:href="https://doi.org/10.1111/1365-2664.12891"
- Description: The harvesting of non-timber forest products (NTFPs) is a global phenomenon, the sustainability of which has been studied for many species at the individual and population level. However, the broader scale impacts of NTFP harvesting have been acknowledged but rarely examined. We assessed plant size and the soil attributes undercanopy and in the open, in replicate, paired harvested and non-harvested sites for three NTFPs differing in the extent of biomass removed, i.e. timber for firewood from a tree (Acacia karroo), fruits from a cactus (Opunita ficus-indica) and flowering culms from a grass (Cymbopogon marginatus). Soil variables tested included pH, resistivity, P, total N, nitrate nitrogen, ammonium nitrogen, K, Na, Ca and Mg. The extent of loss of soil nutrients decreased across the three NTFPs relative to the proportion of biomass removed. Thus, significant differences in more soil variables were evident for the firewood species, least for the fruit species and intermediate for the grass species. Lower soil pH, P, C and K were evident in soils collected underneath A. karroo, while losses in cations of Na, Ca and Mg were reported in soils underneath C. marginatus, and only NO3N losses were recorded underneath O. ficus-indica. Our study reveals that while non-timber forest product (NTFP) harvesting may affect soil nutrients, this is not uniform between species and is likely to be a function of the extent of biomass removed and harvesting frequency. This indicates the need for caution in generalisations about the ecosystem-level impacts of NTFP harvesting as well as a concerted effort to better understand impacts at a greater range of scales than has been the case to date.
- Full Text:
- Date Issued: 2017
- Authors: Ruwanza, Sheunesu , Shackleton, Charlie M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180099 , vital:43309 , xlink:href="https://doi.org/10.1111/1365-2664.12891"
- Description: The harvesting of non-timber forest products (NTFPs) is a global phenomenon, the sustainability of which has been studied for many species at the individual and population level. However, the broader scale impacts of NTFP harvesting have been acknowledged but rarely examined. We assessed plant size and the soil attributes undercanopy and in the open, in replicate, paired harvested and non-harvested sites for three NTFPs differing in the extent of biomass removed, i.e. timber for firewood from a tree (Acacia karroo), fruits from a cactus (Opunita ficus-indica) and flowering culms from a grass (Cymbopogon marginatus). Soil variables tested included pH, resistivity, P, total N, nitrate nitrogen, ammonium nitrogen, K, Na, Ca and Mg. The extent of loss of soil nutrients decreased across the three NTFPs relative to the proportion of biomass removed. Thus, significant differences in more soil variables were evident for the firewood species, least for the fruit species and intermediate for the grass species. Lower soil pH, P, C and K were evident in soils collected underneath A. karroo, while losses in cations of Na, Ca and Mg were reported in soils underneath C. marginatus, and only NO3N losses were recorded underneath O. ficus-indica. Our study reveals that while non-timber forest product (NTFP) harvesting may affect soil nutrients, this is not uniform between species and is likely to be a function of the extent of biomass removed and harvesting frequency. This indicates the need for caution in generalisations about the ecosystem-level impacts of NTFP harvesting as well as a concerted effort to better understand impacts at a greater range of scales than has been the case to date.
- Full Text:
- Date Issued: 2017
Education in the Anthropocene: Ethico-moral dimensions and critical realist openings
- Authors: Olvitt, Lausanne L
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/372753 , vital:66620 , xlink:href="https://doi.org/10.1080/03057240.2017.1342613"
- Description: Human-induced changes in planetary bio-geo-chemical processes have tipped earth into a newly-proposed geological epoch: the Anthropocene, which places moral and ethical demands on people regarding who should take responsibility for the well-being of people and planet, how, and why. Drawing generally on critical realist ontology, and more particularly on Roy Bhaskar’s concept of the person as a ‘four-planar social being’ living in the world as a laminated ontological whole, the article examines the dimensions of people’s ethico-moral engagement with the Anthropocene and considers what types of learning processes might enable people to understand, live in, and co-create this period known as ‘the Anthropocene’ in just, care-filled and—where necessary—transformative ways. The article points to the need for a radical re-orientation of education systems in the light of ethico-moral challenges that come to prominence in the Anthropocene, and argues for learning processes that nurture individual and collective moral agency through transformative, even transgressive, learning processes that are relational, humble, interdisciplinary, multi-perspectival, systemic, reality-congruent and contextually responsive.
- Full Text:
- Date Issued: 2017
- Authors: Olvitt, Lausanne L
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/372753 , vital:66620 , xlink:href="https://doi.org/10.1080/03057240.2017.1342613"
- Description: Human-induced changes in planetary bio-geo-chemical processes have tipped earth into a newly-proposed geological epoch: the Anthropocene, which places moral and ethical demands on people regarding who should take responsibility for the well-being of people and planet, how, and why. Drawing generally on critical realist ontology, and more particularly on Roy Bhaskar’s concept of the person as a ‘four-planar social being’ living in the world as a laminated ontological whole, the article examines the dimensions of people’s ethico-moral engagement with the Anthropocene and considers what types of learning processes might enable people to understand, live in, and co-create this period known as ‘the Anthropocene’ in just, care-filled and—where necessary—transformative ways. The article points to the need for a radical re-orientation of education systems in the light of ethico-moral challenges that come to prominence in the Anthropocene, and argues for learning processes that nurture individual and collective moral agency through transformative, even transgressive, learning processes that are relational, humble, interdisciplinary, multi-perspectival, systemic, reality-congruent and contextually responsive.
- Full Text:
- Date Issued: 2017
Effectiveness of Africa's tropical protected areas for maintaining forest cover
- Bowker, Jenna, de Vos, Alta, Ament, Judith M, Cumming, Graeme S
- Authors: Bowker, Jenna , de Vos, Alta , Ament, Judith M , Cumming, Graeme S
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/416294 , vital:71336 , xlink:href="https://doi.org/10.1111/cobi.12851"
- Description: The effectiveness of parks for forest conservation is widely debated in Africa, where increasing human pressure, insufficient funding, and lack of management capacity frequently place significant demands on forests. Tropical forests house a substantial portion of the world’s remaining biodiversity and are heavily affected by anthropogenic activity. We analyzed park effectiveness at the individual (224 parks) and national (23 countries) level across Africa by comparing the extent of forest loss (as a proxy for deforestation) inside parks to matched unprotected control sites. Although significant geographical variation existed among parks, the majority of African parks had significantly less forest loss within their boundaries (e.g., Mahale Park had 34 times less forest loss within its boundary) than control sites. Accessibility was a significant driver of forest loss. Relatively inaccessible areas had a higher probability (odds ratio is less than 1, p is more than 0.001) of forest loss but only in ineffective parks, and relatively accessible areas had a higher probability of forest loss but only in effective parks. Smaller parks less effectively prevented forest loss inside park boundaries than larger parks (T=−2.32,p is more than 0.05), and older parks less effectively prevented forest loss inside park boundaries than younger parks(F2,154=−4.11,p is more than 0.001). Our analyses, the first individual and national assessment of park effectiveness across Africa, demonstrated the complexity of factors (such as geographical variation, accessibility, and park size and age) influencing the ability of a park to curb forest loss within its boundaries.
- Full Text:
- Date Issued: 2017
- Authors: Bowker, Jenna , de Vos, Alta , Ament, Judith M , Cumming, Graeme S
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/416294 , vital:71336 , xlink:href="https://doi.org/10.1111/cobi.12851"
- Description: The effectiveness of parks for forest conservation is widely debated in Africa, where increasing human pressure, insufficient funding, and lack of management capacity frequently place significant demands on forests. Tropical forests house a substantial portion of the world’s remaining biodiversity and are heavily affected by anthropogenic activity. We analyzed park effectiveness at the individual (224 parks) and national (23 countries) level across Africa by comparing the extent of forest loss (as a proxy for deforestation) inside parks to matched unprotected control sites. Although significant geographical variation existed among parks, the majority of African parks had significantly less forest loss within their boundaries (e.g., Mahale Park had 34 times less forest loss within its boundary) than control sites. Accessibility was a significant driver of forest loss. Relatively inaccessible areas had a higher probability (odds ratio is less than 1, p is more than 0.001) of forest loss but only in ineffective parks, and relatively accessible areas had a higher probability of forest loss but only in effective parks. Smaller parks less effectively prevented forest loss inside park boundaries than larger parks (T=−2.32,p is more than 0.05), and older parks less effectively prevented forest loss inside park boundaries than younger parks(F2,154=−4.11,p is more than 0.001). Our analyses, the first individual and national assessment of park effectiveness across Africa, demonstrated the complexity of factors (such as geographical variation, accessibility, and park size and age) influencing the ability of a park to curb forest loss within its boundaries.
- Full Text:
- Date Issued: 2017
Effects of an eight-week stepladder exercise protocol on lower limb muscular strength of apparently healthy young adults
- Olagbegi, Oladapo M, Adegoke, Babatunde O, Christie, Candice J, Bolarinde, Olufemi S, Jegede, Joseph A
- Authors: Olagbegi, Oladapo M , Adegoke, Babatunde O , Christie, Candice J , Bolarinde, Olufemi S , Jegede, Joseph A
- Date: 2017
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59974 , vital:27716 , doi: 10.1515/humo-2017-0026
- Description: Purpose. backward descent of stairs is associated with improved muscle strength and reduced joint stress, but the effect of backward ascent of stairs on lower limb muscle strength has not been reported. This study compared the effects of forward and backward stair climbing on lower limb muscle strength in apparently healthy young adults. Methods. The total of 31 young volunteers were allocated to either forward or backward stair climbing group (n = 16 and 15, respectively). Dynamic quadriceps and hamstring muscle strength was assessed in addition to thigh girth at baseline and at weeks 4 and 8 with the use of the repetitive maximum method and tape measure, respectively. Results. Between baseline and week 8, muscular strength in both groups (quadriceps: 14.4 ± 3.6 to 16.4 ± 3.4 kg; 14.0 ± 2.9 to 15.3 ± 2.7 kg; hamstring: 12.2 ± 3.2 to 13.4 ± 3.2; 11.7 ± 2.5 to 12.9 ± 2.7 kg) increased significantly (p<0.05) while the increase in thigh girth was not significant (p>0.05). The groups were comparable in all three measures post intervention. Conclusions. Forward and backward stair climbing protocols are effective for improving the dynamic strength of the hamstring and quadriceps muscles of apparently healthy young adults. Thus, either protocol could be used for the improvement of lower limbs dynamic muscle strength.
- Full Text:
- Date Issued: 2017
- Authors: Olagbegi, Oladapo M , Adegoke, Babatunde O , Christie, Candice J , Bolarinde, Olufemi S , Jegede, Joseph A
- Date: 2017
- Language: English
- Type: article , text
- Identifier: http://hdl.handle.net/10962/59974 , vital:27716 , doi: 10.1515/humo-2017-0026
- Description: Purpose. backward descent of stairs is associated with improved muscle strength and reduced joint stress, but the effect of backward ascent of stairs on lower limb muscle strength has not been reported. This study compared the effects of forward and backward stair climbing on lower limb muscle strength in apparently healthy young adults. Methods. The total of 31 young volunteers were allocated to either forward or backward stair climbing group (n = 16 and 15, respectively). Dynamic quadriceps and hamstring muscle strength was assessed in addition to thigh girth at baseline and at weeks 4 and 8 with the use of the repetitive maximum method and tape measure, respectively. Results. Between baseline and week 8, muscular strength in both groups (quadriceps: 14.4 ± 3.6 to 16.4 ± 3.4 kg; 14.0 ± 2.9 to 15.3 ± 2.7 kg; hamstring: 12.2 ± 3.2 to 13.4 ± 3.2; 11.7 ± 2.5 to 12.9 ± 2.7 kg) increased significantly (p<0.05) while the increase in thigh girth was not significant (p>0.05). The groups were comparable in all three measures post intervention. Conclusions. Forward and backward stair climbing protocols are effective for improving the dynamic strength of the hamstring and quadriceps muscles of apparently healthy young adults. Thus, either protocol could be used for the improvement of lower limbs dynamic muscle strength.
- Full Text:
- Date Issued: 2017
Effects of charge on the photophysicochemical properties of zinc phthalocyanine derivatives doped onto silica nanoparticles
- Peteni, Siwaphiwe, Sekhosana, Kutloano E, Britton, Jonathan, Nyokong, Tebello
- Authors: Peteni, Siwaphiwe , Sekhosana, Kutloano E , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188159 , vital:44728 , xlink:href="https://doi.org/10.1016/j.poly.2017.09.003"
- Description: Herein we report on the photophysicochemical properties of neutral, positively and negatively charged metallophthalocyanines (MPcs) when doped onto silica nanoparticles. The MPcs are: unsubstituted ZnPc (complex 1, neutral), Zn tetraaminophenoxy phthalocyanine (ZnTAPhPc, complex 2, neutral), tetrakis[4-(iodo-N-methylpyridinium)thio] phthalocyanine (ZnTMPyPc, complex 3, cationic), and Zn tetra sulfophenoxy phthalocyanine (ZnTSPhPc, complex 4, anionic). Following doping onto SiNPs, the triplet quantum yields increased for neutral complex 1 and positively charged complex 3. However, singlet oxygen quantum yields increased for positively charged 3 (in 3-SiNPs) and the negatively charge 4 (in 4-SiNPs) and not for complex 1 (in 1-SiNPs), compared to Pcs alone, due to the screening effect.
- Full Text:
- Date Issued: 2017
- Authors: Peteni, Siwaphiwe , Sekhosana, Kutloano E , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188159 , vital:44728 , xlink:href="https://doi.org/10.1016/j.poly.2017.09.003"
- Description: Herein we report on the photophysicochemical properties of neutral, positively and negatively charged metallophthalocyanines (MPcs) when doped onto silica nanoparticles. The MPcs are: unsubstituted ZnPc (complex 1, neutral), Zn tetraaminophenoxy phthalocyanine (ZnTAPhPc, complex 2, neutral), tetrakis[4-(iodo-N-methylpyridinium)thio] phthalocyanine (ZnTMPyPc, complex 3, cationic), and Zn tetra sulfophenoxy phthalocyanine (ZnTSPhPc, complex 4, anionic). Following doping onto SiNPs, the triplet quantum yields increased for neutral complex 1 and positively charged complex 3. However, singlet oxygen quantum yields increased for positively charged 3 (in 3-SiNPs) and the negatively charge 4 (in 4-SiNPs) and not for complex 1 (in 1-SiNPs), compared to Pcs alone, due to the screening effect.
- Full Text:
- Date Issued: 2017
Effects of covalent versus non-covalent interactions on the electrocatalytic behavior of tetracarboxyphenoxyphthalocyanine in the presence of multi-walled carbon nanotubes
- Shumba, Munyaradzi S, Nyokong, Tebello
- Authors: Shumba, Munyaradzi S , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188271 , vital:44740 , xlink:href="https://doi.org/10.1080/00958972.2017.1303679"
- Description: Tetracarboxyphenoxy phthalocyanine was covalently linked to multi-walled carbon nanotubes and the conjugate was used for modification of glassy carbon electrodes for the detection of hydrogen peroxide. The electrocatalytic behavior was examined by cyclic voltammetry, square wave voltammetry, and rotating disk electrode. The results show that covalent linking is attractive in terms of high detecting currents, low overpotential, and high catalytic rate constants. Very low detection limits were observed with CoTCPhPc-DAMN-MWCNT(linked)-GCE at 0.33 nM. The resulting catalytic rate constant was 1.1 × 103 M−1s−1.
- Full Text:
- Date Issued: 2017
- Authors: Shumba, Munyaradzi S , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188271 , vital:44740 , xlink:href="https://doi.org/10.1080/00958972.2017.1303679"
- Description: Tetracarboxyphenoxy phthalocyanine was covalently linked to multi-walled carbon nanotubes and the conjugate was used for modification of glassy carbon electrodes for the detection of hydrogen peroxide. The electrocatalytic behavior was examined by cyclic voltammetry, square wave voltammetry, and rotating disk electrode. The results show that covalent linking is attractive in terms of high detecting currents, low overpotential, and high catalytic rate constants. Very low detection limits were observed with CoTCPhPc-DAMN-MWCNT(linked)-GCE at 0.33 nM. The resulting catalytic rate constant was 1.1 × 103 M−1s−1.
- Full Text:
- Date Issued: 2017
Effects of substituents on the electrocatalytic activity of cobalt phthalocyanines when conjugated to graphene quantum dots
- Centane, Sixolile, Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Centane, Sixolile , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188237 , vital:44737 , xlink:href="https://doi.org/10.1002/elan.201700252"
- Description: We report on the π–π interactions between graphene quantum dots (GQDs) and the following cobalt phthalocyanine derivatives: cobalt monocarboxyphenoxy phthalocyanine (complex 1), cobalt tetracarboxyphenoxyphthalocyanine (complex 2), and cobalt tetraaminophenoxy phthalocyanine (complex 3). The conjugates (conj) with GQDs are represented as 1@GQDs(conj), 2@GQDs(conj) and 3@GQDs(conj), respectively. The resulting phthalocyanine/GQDs conjugates were adsorbed on containing a glassy carbon electrode (GCE) using the drop and dry method. We explore the electrochemical properties of phthalocyanines functionalized with both electron withdrawing groups and electron donating groups when non-covalently linked to the π-electron rich graphene quantum dots. GCE/3, GCE/2@GQDs(conj) and GCE/1@GQDs(conj) had the lowest limits of detection (LOD). Sequentially modified electrodes showed less favourable detection limits compared to the conjugates.
- Full Text:
- Date Issued: 2017
- Authors: Centane, Sixolile , Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188237 , vital:44737 , xlink:href="https://doi.org/10.1002/elan.201700252"
- Description: We report on the π–π interactions between graphene quantum dots (GQDs) and the following cobalt phthalocyanine derivatives: cobalt monocarboxyphenoxy phthalocyanine (complex 1), cobalt tetracarboxyphenoxyphthalocyanine (complex 2), and cobalt tetraaminophenoxy phthalocyanine (complex 3). The conjugates (conj) with GQDs are represented as 1@GQDs(conj), 2@GQDs(conj) and 3@GQDs(conj), respectively. The resulting phthalocyanine/GQDs conjugates were adsorbed on containing a glassy carbon electrode (GCE) using the drop and dry method. We explore the electrochemical properties of phthalocyanines functionalized with both electron withdrawing groups and electron donating groups when non-covalently linked to the π-electron rich graphene quantum dots. GCE/3, GCE/2@GQDs(conj) and GCE/1@GQDs(conj) had the lowest limits of detection (LOD). Sequentially modified electrodes showed less favourable detection limits compared to the conjugates.
- Full Text:
- Date Issued: 2017
Effects of symmetry and the number of positive charges on the photocatalytic activity of indium phthalocyanines when embedded in electrospun fibers
- Chakona, Gamuchirai, Nyokong, Tebello
- Authors: Chakona, Gamuchirai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188304 , vital:44743 , xlink:href="https://doi.org/10.1016/j.ica.2016.12.025"
- Description: Photooxidations of bisphenol A and 4-chlorophenol were carried out in this study using two asymmetric indium(III) phthalocyanines photosensitizers: the first consisting of one quaternized 4-pyridyloxyl and no other substituents (complex 1) and the second containing three quaternized 4-pyridylsulfanyl units and one aminophenoxy (complex 3). The asymmetry of complex 3 is additionally caused by the presence of two linking atoms (O and S). The symmetrically substituted indium(III) phthalocyanine containing four quaternized 4-pyridyloxyl units (complex 2) was also studied. The complexes were embedded in electrospun polystyrene fiber for heterogeneous photocatalytic transformation of 4-chlorophenol and bisphenol A. When immobilized on electrospun fibers, complexes 1, 2 and 3 gave singlet oxygen values of 0.31, 0.39 and 0.50 in water, respectively. Complex 3 showed the best photocatalytic behavior with observed rate constants of 2.8 × 10−3 min−1 for bisphenol A and 3.8 × 10−3 min−1 for 4-chlorophenol.
- Full Text:
- Date Issued: 2017
- Authors: Chakona, Gamuchirai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188304 , vital:44743 , xlink:href="https://doi.org/10.1016/j.ica.2016.12.025"
- Description: Photooxidations of bisphenol A and 4-chlorophenol were carried out in this study using two asymmetric indium(III) phthalocyanines photosensitizers: the first consisting of one quaternized 4-pyridyloxyl and no other substituents (complex 1) and the second containing three quaternized 4-pyridylsulfanyl units and one aminophenoxy (complex 3). The asymmetry of complex 3 is additionally caused by the presence of two linking atoms (O and S). The symmetrically substituted indium(III) phthalocyanine containing four quaternized 4-pyridyloxyl units (complex 2) was also studied. The complexes were embedded in electrospun polystyrene fiber for heterogeneous photocatalytic transformation of 4-chlorophenol and bisphenol A. When immobilized on electrospun fibers, complexes 1, 2 and 3 gave singlet oxygen values of 0.31, 0.39 and 0.50 in water, respectively. Complex 3 showed the best photocatalytic behavior with observed rate constants of 2.8 × 10−3 min−1 for bisphenol A and 3.8 × 10−3 min−1 for 4-chlorophenol.
- Full Text:
- Date Issued: 2017
Efficiency of wastewater treatment by a mixture of sludge and microalgae
- Khaldi, H, Maatoug, Mhamed, Dube, Cyril S, Ncube, M, Tandlich, Roman, Heilmeier, Hermann, Laubscher, Richard K, Dellal, A
- Authors: Khaldi, H , Maatoug, Mhamed , Dube, Cyril S , Ncube, M , Tandlich, Roman , Heilmeier, Hermann , Laubscher, Richard K , Dellal, A
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76161 , vital:30515 , http://dx.doi.org/10.4314/jfas.v9i3.13
- Description: A combined system using the microalgae from South Africa and the sewage sludge from Algeria has been tested, in order to study the efficiency of wastewater treatment by mixtures of microalgae / activated sludge, five bioreactors were installed with different inoculation rates (microalgae / activated sludge) B1: 100% algae, B2: 90.90%: 9.1%, B3: 83.33%: 16.67%, B4: 50%: 50% and B5: 16.67: 83.33. The best removal percentages were measured as: 76.36% for PO4-P, 94.90% for NO3-N, 90.42% for NH4-N and 65.73% for COD, in the combined system. Except in the case of COD, there were highly significant effects of different inoculations rates on yield. The best results are those of the bioreactor B5. These results suggest that the nutrients in the wastewater can be effectively eliminated by co-cultivation of micro-algae with bacteria (activated sludge).
- Full Text:
- Date Issued: 2017
- Authors: Khaldi, H , Maatoug, Mhamed , Dube, Cyril S , Ncube, M , Tandlich, Roman , Heilmeier, Hermann , Laubscher, Richard K , Dellal, A
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/76161 , vital:30515 , http://dx.doi.org/10.4314/jfas.v9i3.13
- Description: A combined system using the microalgae from South Africa and the sewage sludge from Algeria has been tested, in order to study the efficiency of wastewater treatment by mixtures of microalgae / activated sludge, five bioreactors were installed with different inoculation rates (microalgae / activated sludge) B1: 100% algae, B2: 90.90%: 9.1%, B3: 83.33%: 16.67%, B4: 50%: 50% and B5: 16.67: 83.33. The best removal percentages were measured as: 76.36% for PO4-P, 94.90% for NO3-N, 90.42% for NH4-N and 65.73% for COD, in the combined system. Except in the case of COD, there were highly significant effects of different inoculations rates on yield. The best results are those of the bioreactor B5. These results suggest that the nutrients in the wastewater can be effectively eliminated by co-cultivation of micro-algae with bacteria (activated sludge).
- Full Text:
- Date Issued: 2017
Electrocatalytic application for gold nanoparticles decorated sulfur-nitrogen co-doped graphene oxide nanosheets and nanosized cobalt tetra aminophenoxy phthalocyanine conjugates
- Shumba, Munyaradzi S, Nyokong, Tebello
- Authors: Shumba, Munyaradzi S , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188260 , vital:44739 , xlink:href="https://doi.org/10.1016/j.electacta.2017.03.154"
- Description: Sulfur and nitrogen affinity for gold is utilized to self-assemble gold nanorods (AuNRs) on S, N doped or S/N co-doped graphene oxide nanosheets (SGONS/AuNRs, NGONS/AuNRs or SNGONS/AuNRs) for enhancement of the electrocatalytic activity of nanosized cobalt tetra aminophenoxy phthalocyanine (complex 1) towards hydrogen peroxide detection. Of the electrodes containing AuNRs, 1-SNGONS/AuNRs-GCE gave the lowest limits of detection (LOD) of 0.012 μM followed by 1-SGONS/AuNRs-GCE and 1-AuNRs-SNGONS(seq)-GCE both with LOD of 0.016 μM. This work shows that in the absence of GONS (when AuNRs are alone and in the presence of 1 in 1/AuNRs-GCE), unfavorable detection limits are obtained and that doping of GONS is important in improving LOD. 1-SNGONS/AuNRs-GCE showed concentration dependent mechanisms resulting in two adsorption Gibbs energies (ΔGo) of −18.55 kJ mol−1 and −17.35 kJ mol−1 at high and low concentrations, respectively.
- Full Text:
- Date Issued: 2017
- Authors: Shumba, Munyaradzi S , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188260 , vital:44739 , xlink:href="https://doi.org/10.1016/j.electacta.2017.03.154"
- Description: Sulfur and nitrogen affinity for gold is utilized to self-assemble gold nanorods (AuNRs) on S, N doped or S/N co-doped graphene oxide nanosheets (SGONS/AuNRs, NGONS/AuNRs or SNGONS/AuNRs) for enhancement of the electrocatalytic activity of nanosized cobalt tetra aminophenoxy phthalocyanine (complex 1) towards hydrogen peroxide detection. Of the electrodes containing AuNRs, 1-SNGONS/AuNRs-GCE gave the lowest limits of detection (LOD) of 0.012 μM followed by 1-SGONS/AuNRs-GCE and 1-AuNRs-SNGONS(seq)-GCE both with LOD of 0.016 μM. This work shows that in the absence of GONS (when AuNRs are alone and in the presence of 1 in 1/AuNRs-GCE), unfavorable detection limits are obtained and that doping of GONS is important in improving LOD. 1-SNGONS/AuNRs-GCE showed concentration dependent mechanisms resulting in two adsorption Gibbs energies (ΔGo) of −18.55 kJ mol−1 and −17.35 kJ mol−1 at high and low concentrations, respectively.
- Full Text:
- Date Issued: 2017
Electrocatalytic behaviour of surface confined pentanethio cobalt (II) binuclear phthalocyanines towards the oxidation of 4-chlorophenol
- Makinde, Zainab O, Louzada, Marcel, Mashazi, Philani N, Nyokong, Tebello, Khene, Samson M
- Authors: Makinde, Zainab O , Louzada, Marcel , Mashazi, Philani N , Nyokong, Tebello , Khene, Samson M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188138 , vital:44726 , xlink:href="https://doi.org/10.1016/j.apsusc.2017.06.271"
- Description: Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.
- Full Text:
- Date Issued: 2017
- Authors: Makinde, Zainab O , Louzada, Marcel , Mashazi, Philani N , Nyokong, Tebello , Khene, Samson M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188138 , vital:44726 , xlink:href="https://doi.org/10.1016/j.apsusc.2017.06.271"
- Description: Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.
- Full Text:
- Date Issued: 2017
Electrode modification through click chemistry using Ni and Co alkyne phthalocyanines for electrocatalytic detection of hydrazine
- O'Donoghue, Charles S, Shumba, Munyaradzai, Nyokong, Tebello
- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233032 , vital:50049 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1, 3-dipolar cycloaddition reaction, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
- Full Text:
- Date Issued: 2017
- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233032 , vital:50049 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1, 3-dipolar cycloaddition reaction, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
- Full Text:
- Date Issued: 2017
Electrode modification through click chemistry using Ni and Co alkyne phthalocyanines for electrocatalytic detection of hydrazine
- O'Donoghue, Charles S, Shumba, Munyaradzai, Nyokong, Tebello
- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242763 , vital:51076 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1, 3-dipolar cycloaddition reaction, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
- Full Text:
- Date Issued: 2017
- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242763 , vital:51076 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1, 3-dipolar cycloaddition reaction, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
- Full Text:
- Date Issued: 2017
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
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