MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine
- Mack, John, Mkhize, Scebi, Safonoya, Evgeniya A, Gorbunova, Yulia G, Tsivadze, Aslan Yu, Nyokong, Tebello
- Authors: Mack, John , Mkhize, Scebi , Safonoya, Evgeniya A , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240743 , vital:50867 , xlink:href="https://doi.org/10.1142/S1088424616500322"
- Description: An analysis of the MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine is reported. This study provides a reassessment of an earlier study on the nature of the bands in UV-visible absorption spectra of magnesium and zinc tetra-(15-crown-5-oxanthreno)-phthalocyanine that was based on an analysis of TD-DFT calculations for a series of model complexes with the B3LYP functional. A detailed analysis of MCD spectral data and TD-DFT calculations with the CAM-B3LYP functional for the complete Mg(II) complex provides an additional insight into the optical properties and electronic structures of tetra-(15-crown-5-oxanthreno)-phthalocyanines. Thus, the bands in the Q-band region are reassigned as being due exclusively to the Q transition of Gouterman’s 4-orbital model, since intense pseudo-A1𝒜1 terms are observed in the MCD spectrum in a spectral region that had previously been assigned as charge transfer bands.
- Full Text:
- Date Issued: 2016
- Authors: Mack, John , Mkhize, Scebi , Safonoya, Evgeniya A , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240743 , vital:50867 , xlink:href="https://doi.org/10.1142/S1088424616500322"
- Description: An analysis of the MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine is reported. This study provides a reassessment of an earlier study on the nature of the bands in UV-visible absorption spectra of magnesium and zinc tetra-(15-crown-5-oxanthreno)-phthalocyanine that was based on an analysis of TD-DFT calculations for a series of model complexes with the B3LYP functional. A detailed analysis of MCD spectral data and TD-DFT calculations with the CAM-B3LYP functional for the complete Mg(II) complex provides an additional insight into the optical properties and electronic structures of tetra-(15-crown-5-oxanthreno)-phthalocyanines. Thus, the bands in the Q-band region are reassigned as being due exclusively to the Q transition of Gouterman’s 4-orbital model, since intense pseudo-A1𝒜1 terms are observed in the MCD spectrum in a spectral region that had previously been assigned as charge transfer bands.
- Full Text:
- Date Issued: 2016
Measuring discrimination experienced by people with a mental illness
- Brohan, Elaine, Thornicroft, Graham, Rüsch, Nicolas, Lasalvia, Antonio, Campbell, Megan, Yalçınkaya-Alkar, Özden, Lanfredi, Mariangela, Ochoa, Susana, Üçok, Alp, Tomás, Catarina, Fadipe, Babatunde, Sebes, Julia, Fiorillo, Andrea, Sampogna, Gaia, Paula, Cristiane Silvestre, Valverde, Leonadis, Schomerus, Georg, Klemm, Pia, Ouali, Uta, Castelein, Stynke, Alexová, Aneta, Oexle, Nathalie, Guimarães, Patrícia Neves, Sportel, Bouwina Esther, Chang, Chih-Cheng, Li, Jie, Shanthi, Chilasagaram, Reneses, Blanca, Bakolis, Ioannis, Evans-Lacko, Sarah
- Authors: Brohan, Elaine , Thornicroft, Graham , Rüsch, Nicolas , Lasalvia, Antonio , Campbell, Megan , Yalçınkaya-Alkar, Özden , Lanfredi, Mariangela , Ochoa, Susana , Üçok, Alp , Tomás, Catarina , Fadipe, Babatunde , Sebes, Julia , Fiorillo, Andrea , Sampogna, Gaia , Paula, Cristiane Silvestre , Valverde, Leonadis , Schomerus, Georg , Klemm, Pia , Ouali, Uta , Castelein, Stynke , Alexová, Aneta , Oexle, Nathalie , Guimarães, Patrícia Neves , Sportel, Bouwina Esther , Chang, Chih-Cheng , Li, Jie , Shanthi, Chilasagaram , Reneses, Blanca , Bakolis, Ioannis , Evans-Lacko, Sarah
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/302498 , vital:58202 , xlink:href="https://doi.org/10.1017/S0033291722000630"
- Description: Background: The Discrimination and Stigma Scale (DISC) is a patient-reported outcome measure which assesses experiences of discrimination among persons with a mental illness globally. Methods: This study evaluated whether the psychometric properties of a short-form version, DISC-Ultra Short (DISCUS) (11-item), could be replicated in a sample of people with a wide range of mental disorders from 21 sites in 15 countries/territories, across six global regions. The frequency of experienced discrimination was reported. Scaling assumptions (confirmatory factor analysis, inter-item and item-total correlations), reliability (internal consistency) and validity (convergent validity, known groups method) were investigated in each region, and by diagnosis group. Results: 1195 people participated. The most frequently reported experiences of discrimination were being shunned or avoided at work (48.7%) and discrimination in making or keeping friends (47.2%). Confirmatory factor analysis supported a unidimensional model across all six regions and five diagnosis groups. Convergent validity was confirmed in the total sample and within all regions [ Internalised Stigma of Mental Illness (ISMI-10): 0.28–0.67, stopping self: 0.54–0.72, stigma consciousness: −0.32–0.57], as was internal consistency reliability (α = 0.74–0.84). Known groups validity was established in the global sample with levels of experienced discrimination significantly higher for those experiencing higher depression [Patient Health Questionnaire (PHQ)-2: p more than 0.001], lower mental wellbeing [Warwick-Edinburgh Well-being Scale (WEMWBS): p is less than 0.001], higher suicidal ideation [Beck Hopelessness Scale (BHS)-4: p is less than 0.001] and higher risk of suicidal behaviour [Suicidal Ideation Attributes Scale (SIDAS): p is less than 0.001]. Conclusions: The DISCUS is a reliable and valid unidimensional measure of experienced discrimination for use in global settings with similar properties to the longer DISC. It offers a brief assessment of experienced discrimination for use in clinical and research settings.
- Full Text:
- Date Issued: 2022
- Authors: Brohan, Elaine , Thornicroft, Graham , Rüsch, Nicolas , Lasalvia, Antonio , Campbell, Megan , Yalçınkaya-Alkar, Özden , Lanfredi, Mariangela , Ochoa, Susana , Üçok, Alp , Tomás, Catarina , Fadipe, Babatunde , Sebes, Julia , Fiorillo, Andrea , Sampogna, Gaia , Paula, Cristiane Silvestre , Valverde, Leonadis , Schomerus, Georg , Klemm, Pia , Ouali, Uta , Castelein, Stynke , Alexová, Aneta , Oexle, Nathalie , Guimarães, Patrícia Neves , Sportel, Bouwina Esther , Chang, Chih-Cheng , Li, Jie , Shanthi, Chilasagaram , Reneses, Blanca , Bakolis, Ioannis , Evans-Lacko, Sarah
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/302498 , vital:58202 , xlink:href="https://doi.org/10.1017/S0033291722000630"
- Description: Background: The Discrimination and Stigma Scale (DISC) is a patient-reported outcome measure which assesses experiences of discrimination among persons with a mental illness globally. Methods: This study evaluated whether the psychometric properties of a short-form version, DISC-Ultra Short (DISCUS) (11-item), could be replicated in a sample of people with a wide range of mental disorders from 21 sites in 15 countries/territories, across six global regions. The frequency of experienced discrimination was reported. Scaling assumptions (confirmatory factor analysis, inter-item and item-total correlations), reliability (internal consistency) and validity (convergent validity, known groups method) were investigated in each region, and by diagnosis group. Results: 1195 people participated. The most frequently reported experiences of discrimination were being shunned or avoided at work (48.7%) and discrimination in making or keeping friends (47.2%). Confirmatory factor analysis supported a unidimensional model across all six regions and five diagnosis groups. Convergent validity was confirmed in the total sample and within all regions [ Internalised Stigma of Mental Illness (ISMI-10): 0.28–0.67, stopping self: 0.54–0.72, stigma consciousness: −0.32–0.57], as was internal consistency reliability (α = 0.74–0.84). Known groups validity was established in the global sample with levels of experienced discrimination significantly higher for those experiencing higher depression [Patient Health Questionnaire (PHQ)-2: p more than 0.001], lower mental wellbeing [Warwick-Edinburgh Well-being Scale (WEMWBS): p is less than 0.001], higher suicidal ideation [Beck Hopelessness Scale (BHS)-4: p is less than 0.001] and higher risk of suicidal behaviour [Suicidal Ideation Attributes Scale (SIDAS): p is less than 0.001]. Conclusions: The DISCUS is a reliable and valid unidimensional measure of experienced discrimination for use in global settings with similar properties to the longer DISC. It offers a brief assessment of experienced discrimination for use in clinical and research settings.
- Full Text:
- Date Issued: 2022
Mechanisms and indicators for assessing the impact of biofuel feedstock production on ecosystem services
- Gasparatos, Alexandros, Romeu-Dalmau, Carla, von Maltitz, Graham P, Johnson, Francis X, Shackleton, Charlie M, Jarzebski, Marcin P, Jumbe, Charles, Ochieng, Caroline, Mudombi, Shakespear, Nyambane, Anne, Willis, Katherine J
- Authors: Gasparatos, Alexandros , Romeu-Dalmau, Carla , von Maltitz, Graham P , Johnson, Francis X , Shackleton, Charlie M , Jarzebski, Marcin P , Jumbe, Charles , Ochieng, Caroline , Mudombi, Shakespear , Nyambane, Anne , Willis, Katherine J
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181368 , vital:43727 , xlink:href="https://doi.org/10.1016/j.biombioe.2018.01.024"
- Description: Biofuel feedstock production can be a significant driver of landscape modification, ecosystem change and biodiversity loss. There is growing body of literature that shows how biofuel landscapes provide various ecosystem services (e.g., feedstock for fuel, carbon sequestration) and compromise other ecosystem services (e.g., food, freshwater services). These effects are context-specific and depend largely on prior land use conditions and feedstock production practices. Changes in the flow of ecosystem services due to the conversion of natural and agricultural areas can have ripple effects on human wellbeing. Despite some recent attempts to apply to biofuel settings concepts and methods rooted in the ecosystem services literature, this is the exception rather than the rule within both the biofuel and the ecosystem services research communities. This paper synthesizes the current knowledge about the impact of biofuels on ecosystem services. It focuses especially on the feedstock production phase and outlines the main mechanisms through which landscape conversion affects the provisions of ecosystem services. It proposes conceptually coherent indicators to reflect these mechanisms and offers a critical discussion of key issues at the interface of biofuels and ecosystem services.
- Full Text:
- Date Issued: 2018
- Authors: Gasparatos, Alexandros , Romeu-Dalmau, Carla , von Maltitz, Graham P , Johnson, Francis X , Shackleton, Charlie M , Jarzebski, Marcin P , Jumbe, Charles , Ochieng, Caroline , Mudombi, Shakespear , Nyambane, Anne , Willis, Katherine J
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181368 , vital:43727 , xlink:href="https://doi.org/10.1016/j.biombioe.2018.01.024"
- Description: Biofuel feedstock production can be a significant driver of landscape modification, ecosystem change and biodiversity loss. There is growing body of literature that shows how biofuel landscapes provide various ecosystem services (e.g., feedstock for fuel, carbon sequestration) and compromise other ecosystem services (e.g., food, freshwater services). These effects are context-specific and depend largely on prior land use conditions and feedstock production practices. Changes in the flow of ecosystem services due to the conversion of natural and agricultural areas can have ripple effects on human wellbeing. Despite some recent attempts to apply to biofuel settings concepts and methods rooted in the ecosystem services literature, this is the exception rather than the rule within both the biofuel and the ecosystem services research communities. This paper synthesizes the current knowledge about the impact of biofuels on ecosystem services. It focuses especially on the feedstock production phase and outlines the main mechanisms through which landscape conversion affects the provisions of ecosystem services. It proposes conceptually coherent indicators to reflect these mechanisms and offers a critical discussion of key issues at the interface of biofuels and ecosystem services.
- Full Text:
- Date Issued: 2018
Melatonin alters the photodegradation of paracetamol
- Anoopkumar-Dukie, Shailendra, Glass, Beverley D, Walker, Roderick B, Daya, Santylal
- Authors: Anoopkumar-Dukie, Shailendra , Glass, Beverley D , Walker, Roderick B , Daya, Santylal
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184357 , vital:44211 , xlink:href="https://doi.org/10.1211/146080800128735755"
- Description: The effects of melatonin, a known free-radical scavenger, on paracetamol in the presence of UV irradiation was studied by use of HPLC. The experiments were performed in air and nitrogen. The results show that the rate of photodegradation of melatonin is faster in air than in nitrogen whereas that of paracetamol is similar in air and nitrogen. When the two drugs were combined, melatonin retarded the degradation of paracetamol for up to 6h in the presence of nitrogen. However, in the presence of air melatonin rapidly enhances the photodegradation of paracetamol. This study shows that a combination of melatonin and paracetamol in the presence of air and UV irradiation can lead to rapid inactivation of both agents, thus raising important concerns about the possible use of melatonin as sunscreen
- Full Text:
- Date Issued: 2000
- Authors: Anoopkumar-Dukie, Shailendra , Glass, Beverley D , Walker, Roderick B , Daya, Santylal
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184357 , vital:44211 , xlink:href="https://doi.org/10.1211/146080800128735755"
- Description: The effects of melatonin, a known free-radical scavenger, on paracetamol in the presence of UV irradiation was studied by use of HPLC. The experiments were performed in air and nitrogen. The results show that the rate of photodegradation of melatonin is faster in air than in nitrogen whereas that of paracetamol is similar in air and nitrogen. When the two drugs were combined, melatonin retarded the degradation of paracetamol for up to 6h in the presence of nitrogen. However, in the presence of air melatonin rapidly enhances the photodegradation of paracetamol. This study shows that a combination of melatonin and paracetamol in the presence of air and UV irradiation can lead to rapid inactivation of both agents, thus raising important concerns about the possible use of melatonin as sunscreen
- Full Text:
- Date Issued: 2000
Melatonin generates singlet oxygen on laser irradiation but acts as a quencher when irradiated by lamp photolysis
- Maharaj, Deepa S, Molell, H, Antunes, Edith M, Maharaj, Hiren, Maree, D M, Nyokong, Tebello, Glass, Beverley D, Daya, Santy
- Authors: Maharaj, Deepa S , Molell, H , Antunes, Edith M , Maharaj, Hiren , Maree, D M , Nyokong, Tebello , Glass, Beverley D , Daya, Santy
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300335 , vital:57917 , xlink:href="https://doi.org/10.1111/j.1600-079X.2004.00185.x"
- Description: Melatonin, a naturally occurring chemical mediator, although assigned a diverse range of functions, has attracted interest in recent years because of its ability to function as a free radical scavenger. Because of the implications of singlet oxygen in neurotoxicity, the objective of the study was to investigate the ability of melatonin to quench singlet oxygen generated using laser irradiation or lamp photolysis. The results show that melatonin produces radicals upon laser irradation while the lamp photolysis studies show that melatonin is able to scavenge singlet oxygen produced by naphthalene. While melatonin is a free radical scavenger under biological conditions, it acts as a generator of singlet oxygen and or radicals (as ΦΔ is 1.41) when irradiated with laser light, implying that it has the potential to be used in photodynamic therapy in the destruction of tumors.
- Full Text:
- Date Issued: 2005
- Authors: Maharaj, Deepa S , Molell, H , Antunes, Edith M , Maharaj, Hiren , Maree, D M , Nyokong, Tebello , Glass, Beverley D , Daya, Santy
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300335 , vital:57917 , xlink:href="https://doi.org/10.1111/j.1600-079X.2004.00185.x"
- Description: Melatonin, a naturally occurring chemical mediator, although assigned a diverse range of functions, has attracted interest in recent years because of its ability to function as a free radical scavenger. Because of the implications of singlet oxygen in neurotoxicity, the objective of the study was to investigate the ability of melatonin to quench singlet oxygen generated using laser irradiation or lamp photolysis. The results show that melatonin produces radicals upon laser irradation while the lamp photolysis studies show that melatonin is able to scavenge singlet oxygen produced by naphthalene. While melatonin is a free radical scavenger under biological conditions, it acts as a generator of singlet oxygen and or radicals (as ΦΔ is 1.41) when irradiated with laser light, implying that it has the potential to be used in photodynamic therapy in the destruction of tumors.
- Full Text:
- Date Issued: 2005
Melatonin protects against copper‐mediated free radical damage
- Parmar, Paresh, Limson, Janice, Nyokong, Tebello, Daya, Santy
- Authors: Parmar, Paresh , Limson, Janice , Nyokong, Tebello , Daya, Santy
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289617 , vital:56654 , xlink:href=" https://doi.org/10.1034/j.1600-079X.2002.01859.x"
- Description: Copper is an essential trace element which forms an integral component of many enzymes. While trace amounts of copper are needed to sustain life, excess copper is extremely toxic. Copper has been implicated in various neurodegenerative disorders, such as Wilson's and Alzheimer's diseases. Previous studies showed that melatonin, the principle secretory product of the pineal gland, binds Cupric chloride (Cu2+) and that this may have implications in copper-induced neurodegenerative diseases. In the present study, in vitro copper-mediated lipid peroxidation was induced. Melatonin (5 mM) protected against copper-mediated lipid peroxidation in liver homogenates. Electron micrographs of in vivo administered Cu2+ and melatonin show that melatonin affords some protection to rat hepatocytes in the presence of copper. Electrochemical studies performed show that melatonin, in addition to binding Cu2+, may provide protection against copper-mediated free radical damage by binding Cu1+. The findings of these studies provide further evidence for the neuroprotective role of melatonin.
- Full Text:
- Date Issued: 2002
- Authors: Parmar, Paresh , Limson, Janice , Nyokong, Tebello , Daya, Santy
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289617 , vital:56654 , xlink:href=" https://doi.org/10.1034/j.1600-079X.2002.01859.x"
- Description: Copper is an essential trace element which forms an integral component of many enzymes. While trace amounts of copper are needed to sustain life, excess copper is extremely toxic. Copper has been implicated in various neurodegenerative disorders, such as Wilson's and Alzheimer's diseases. Previous studies showed that melatonin, the principle secretory product of the pineal gland, binds Cupric chloride (Cu2+) and that this may have implications in copper-induced neurodegenerative diseases. In the present study, in vitro copper-mediated lipid peroxidation was induced. Melatonin (5 mM) protected against copper-mediated lipid peroxidation in liver homogenates. Electron micrographs of in vivo administered Cu2+ and melatonin show that melatonin affords some protection to rat hepatocytes in the presence of copper. Electrochemical studies performed show that melatonin, in addition to binding Cu2+, may provide protection against copper-mediated free radical damage by binding Cu1+. The findings of these studies provide further evidence for the neuroprotective role of melatonin.
- Full Text:
- Date Issued: 2002
Men in Women’s Clothes
- Authors: Jones, Ward E
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/275658 , vital:55067 , xlink:href="https://doi.org/10.1111/sjp.12394"
- Description: The descriptive phrase that comprises my title can refer both to a pervasive comic trope and a mode of self-expression. There is a tension here, insofar as the comic trope leads us not to take cross-dressing, or drag, seriously. The first half of the comic film Some Like It Hot (1959), with its cross-gender plot and its (sophisticated but) straightforward use of the comic trope of men-in-women’s clothes, appears to fall foul of this tension and to be susceptible to criticism in this regard. However, the film rectifies itself, portraying the cross-dressing relationship which develops through the second half of the film as a potentially meaningful one for both partners. In this article, I interpret the film as inviting its viewers to adopt a (particular kind of) skeptical ironic (that is, Pyrrhonian) attitude toward gender-presentation practices. While the film in no way attempts to discourage us from participating in such practices, it does invite us—through our partiality toward the characters Osgood and Jerry/Daphne, as we follow their budding, transgressive relationship—to acknowledge that a violation of gender-presentation practices can be a meaningful feature of sincere relationships.
- Full Text:
- Date Issued: 2020
- Authors: Jones, Ward E
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/275658 , vital:55067 , xlink:href="https://doi.org/10.1111/sjp.12394"
- Description: The descriptive phrase that comprises my title can refer both to a pervasive comic trope and a mode of self-expression. There is a tension here, insofar as the comic trope leads us not to take cross-dressing, or drag, seriously. The first half of the comic film Some Like It Hot (1959), with its cross-gender plot and its (sophisticated but) straightforward use of the comic trope of men-in-women’s clothes, appears to fall foul of this tension and to be susceptible to criticism in this regard. However, the film rectifies itself, portraying the cross-dressing relationship which develops through the second half of the film as a potentially meaningful one for both partners. In this article, I interpret the film as inviting its viewers to adopt a (particular kind of) skeptical ironic (that is, Pyrrhonian) attitude toward gender-presentation practices. While the film in no way attempts to discourage us from participating in such practices, it does invite us—through our partiality toward the characters Osgood and Jerry/Daphne, as we follow their budding, transgressive relationship—to acknowledge that a violation of gender-presentation practices can be a meaningful feature of sincere relationships.
- Full Text:
- Date Issued: 2020
Meso-and axially-modified IrIIItriarylcorroles with tunable electrocatalytic properties
- Zhang, Xifeng, Wang, Yu, Zhu, Weihua, Mack, John, Soy, Rodah C, Nyokong, Tebello, Liang, Xu
- Authors: Zhang, Xifeng , Wang, Yu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190851 , vital:45034 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: The synthesis of three A2B type Ir(III)triarylcorroles with meso-aryl substituents that provide electron donating (push) and withdrawing (pull) properties and three A3 type IrIIItriphenylcorroles with differing pyridine axial ligands is reported, along with their structural characterization. An analysis of the structure-property relationships in the optical and redox properties has been carried out by comparing their optical spectroscopy and electrochemistry to trends predicted in DFT and TD-DFT calculations. The results demonstrate that A2B type IrIIItriarylcorroles are highly efficient electrocatalyzed oxygen reduction reactions (ORRs) and that their reactivity can be modulated by modulating the electronic structure by changing the nature of the meso-substituent at the B-positions, and even axial pyridine ligands.
- Full Text:
- Date Issued: 2015
- Authors: Zhang, Xifeng , Wang, Yu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190851 , vital:45034 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: The synthesis of three A2B type Ir(III)triarylcorroles with meso-aryl substituents that provide electron donating (push) and withdrawing (pull) properties and three A3 type IrIIItriphenylcorroles with differing pyridine axial ligands is reported, along with their structural characterization. An analysis of the structure-property relationships in the optical and redox properties has been carried out by comparing their optical spectroscopy and electrochemistry to trends predicted in DFT and TD-DFT calculations. The results demonstrate that A2B type IrIIItriarylcorroles are highly efficient electrocatalyzed oxygen reduction reactions (ORRs) and that their reactivity can be modulated by modulating the electronic structure by changing the nature of the meso-substituent at the B-positions, and even axial pyridine ligands.
- Full Text:
- Date Issued: 2015
Metal (Co, Fe) tribenzotetraazachlorin–fullerene conjugates
- Ozoemena, Kenneth I, Mamuru, Solomon A, Fukuda, Takamitsu, Kobayashi, Nagao, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Mamuru, Solomon A , Fukuda, Takamitsu , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263464 , vital:53630 , xlink:href="https://doi.org/10.1016/j.elecom.2009.04.011"
- Description: Novel hexabutylsulphonyltribenzotetraazachlorin–fullerene (C60) complexes of iron (FeHBSTBTAC–C60) and cobalt (CoHBSTBTAC–C60) have been synthesized and their electrochemistry and oxygen reduction reaction (ORR) compared with their octabutylsulphonylphthalocyanine analogues (FeOBSPc and CoOBSPc). It is proved that electron-withdrawing substituents (–SO2Bu and C60) on phthalocyanine macrocycle exhibit distinct impact on the solution electrochemistry of these metallophthalocyanine (MPc) complexes. The more electron-withdrawing C60 substituent suppressed ORR compared to the –SO2Bu in alkaline medium. FeOBSPc showed the best ORR activity involving a direct 4-electron mechanism, a rate constant of ∼1 × 108 cm3 mol−1 s−1 and a Tafel slope of −171 mV dec−1.
- Full Text:
- Date Issued: 2009
- Authors: Ozoemena, Kenneth I , Mamuru, Solomon A , Fukuda, Takamitsu , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263464 , vital:53630 , xlink:href="https://doi.org/10.1016/j.elecom.2009.04.011"
- Description: Novel hexabutylsulphonyltribenzotetraazachlorin–fullerene (C60) complexes of iron (FeHBSTBTAC–C60) and cobalt (CoHBSTBTAC–C60) have been synthesized and their electrochemistry and oxygen reduction reaction (ORR) compared with their octabutylsulphonylphthalocyanine analogues (FeOBSPc and CoOBSPc). It is proved that electron-withdrawing substituents (–SO2Bu and C60) on phthalocyanine macrocycle exhibit distinct impact on the solution electrochemistry of these metallophthalocyanine (MPc) complexes. The more electron-withdrawing C60 substituent suppressed ORR compared to the –SO2Bu in alkaline medium. FeOBSPc showed the best ORR activity involving a direct 4-electron mechanism, a rate constant of ∼1 × 108 cm3 mol−1 s−1 and a Tafel slope of −171 mV dec−1.
- Full Text:
- Date Issued: 2009
Metallophthalocyanine Based Carbon Paste Electrodes for the Determination of 2′, 3′‐Dideoxyinosine
- Ozoemena, Kenneth I, Stefan-van Staden, Raluca-Ioana, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Stefan-van Staden, Raluca-Ioana , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263430 , vital:53627 , xlink:href="https://doi.org/10.1002/elan.200904581"
- Description: Novel electrochemical sensors based on carbon paste impregnated with metallopthalocyanine (MPc, M=Co, Fe) complexes, have been constructed for the assay of anti-HIV drug 2′,3′-dideoxyinosine (didanosine, DDI). Both modified electrodes showed electrocatalytic activity towards the oxidation of dideoxyinosine in phosphate buffer pH 7.4 with a working concentration range of 10−6–10−4 mol/L and a detection limit of 10−7 mol/L magnitude order. The sensor proved to be highly reliable for the assay of the purity of DDI - raw material as well as for the uniformity content test of Videx tablets.
- Full Text:
- Date Issued: 2009
- Authors: Ozoemena, Kenneth I , Stefan-van Staden, Raluca-Ioana , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263430 , vital:53627 , xlink:href="https://doi.org/10.1002/elan.200904581"
- Description: Novel electrochemical sensors based on carbon paste impregnated with metallopthalocyanine (MPc, M=Co, Fe) complexes, have been constructed for the assay of anti-HIV drug 2′,3′-dideoxyinosine (didanosine, DDI). Both modified electrodes showed electrocatalytic activity towards the oxidation of dideoxyinosine in phosphate buffer pH 7.4 with a working concentration range of 10−6–10−4 mol/L and a detection limit of 10−7 mol/L magnitude order. The sensor proved to be highly reliable for the assay of the purity of DDI - raw material as well as for the uniformity content test of Videx tablets.
- Full Text:
- Date Issued: 2009
Metallophthalocyanine catalysed electroreduction of nitrate and nitrite ions in alkaline media
- Chebotareva, Natalia, Nyokong, Tebello
- Authors: Chebotareva, Natalia , Nyokong, Tebello
- Date: 1997
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293301 , vital:57073 , xlink:href="https://doi.org/10.1023/A:1018466021838"
- Description: Copper, cadmium, lead and bismuth (> 5 μg ml−1) are determined by adsorptive cathodic stripping voltammetry (AdCSV) on a mercury film glassy carbon electrode, using catechol, 4-methylcatechol, 4-t-butylcatechol and resorcinol as complexing ligands. Complexes of lead, copper and bismuth with resorcinol showed the largest increase in current with increase in metal concentration, whereas complexes of these metals with 4-t-butylcatechol showed the lowest current response. Cadmium showed a different behaviour from the other three metals in that the highest current response was observed with 4-methylcatechol. The four metals could be determined simultaneously in the presence of resorcinol, although considerable interference was observed between bismuth and copper.
- Full Text: false
- Date Issued: 1997
- Authors: Chebotareva, Natalia , Nyokong, Tebello
- Date: 1997
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293301 , vital:57073 , xlink:href="https://doi.org/10.1023/A:1018466021838"
- Description: Copper, cadmium, lead and bismuth (> 5 μg ml−1) are determined by adsorptive cathodic stripping voltammetry (AdCSV) on a mercury film glassy carbon electrode, using catechol, 4-methylcatechol, 4-t-butylcatechol and resorcinol as complexing ligands. Complexes of lead, copper and bismuth with resorcinol showed the largest increase in current with increase in metal concentration, whereas complexes of these metals with 4-t-butylcatechol showed the lowest current response. Cadmium showed a different behaviour from the other three metals in that the highest current response was observed with 4-methylcatechol. The four metals could be determined simultaneously in the presence of resorcinol, although considerable interference was observed between bismuth and copper.
- Full Text: false
- Date Issued: 1997
Methodological Decisions in Context: The dilemmas and challenges of novice African scholars
- Lupele, Justin, Mwingi, Mweru, Kinyanjui, Felistus, Kimani, Joyce, Kisamba, Christine
- Authors: Lupele, Justin , Mwingi, Mweru , Kinyanjui, Felistus , Kimani, Joyce , Kisamba, Christine
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373734 , vital:66717 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/122698"
- Description: This paper emerges out of a panel discussion during a PhD week and subsequent 8th International Environmental Education Invitation Seminar held at Rhodes University in 2004 and 2005 respectively. It illuminates some insights into our struggles (as novice African researchers) in trying to respond to contextual realities as we research education and social change in African contexts, seeking insight into what counts as legitimate research in this context. The paper considers our struggles at conceptual, methodological, analytical and data generation levels, and in a politics of research. This is done by means of examples drawn from five current doctoral research projects being undertaken in east and southern African regions, using a review framework that represents fairly common dimensions of PhD research. We conclude that research, when defined rigidly within research disciplines/paradigms (as have been defined in some – primarily Western – research trajectories) may fail to take into account African social and contextual realities when applied uncritically. We argue that there is need for researchers in Africa to consider a multiplicity of approaches if research is to be meaningful in, and responsive to, social and contextual realities. In particular, we argue for taking account of socio historical and socio-cultural contexts in creating African epistemology in and through research.
- Full Text:
- Date Issued: 2005
- Authors: Lupele, Justin , Mwingi, Mweru , Kinyanjui, Felistus , Kimani, Joyce , Kisamba, Christine
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/373734 , vital:66717 , xlink:href="https://www.ajol.info/index.php/sajee/article/view/122698"
- Description: This paper emerges out of a panel discussion during a PhD week and subsequent 8th International Environmental Education Invitation Seminar held at Rhodes University in 2004 and 2005 respectively. It illuminates some insights into our struggles (as novice African researchers) in trying to respond to contextual realities as we research education and social change in African contexts, seeking insight into what counts as legitimate research in this context. The paper considers our struggles at conceptual, methodological, analytical and data generation levels, and in a politics of research. This is done by means of examples drawn from five current doctoral research projects being undertaken in east and southern African regions, using a review framework that represents fairly common dimensions of PhD research. We conclude that research, when defined rigidly within research disciplines/paradigms (as have been defined in some – primarily Western – research trajectories) may fail to take into account African social and contextual realities when applied uncritically. We argue that there is need for researchers in Africa to consider a multiplicity of approaches if research is to be meaningful in, and responsive to, social and contextual realities. In particular, we argue for taking account of socio historical and socio-cultural contexts in creating African epistemology in and through research.
- Full Text:
- Date Issued: 2005
Methodological Survey of Simplified TD-DFT Methods for Fast and Accurate Interpretation of UV−Vis−NIR Spectra of Phthalocyanines
- Martynov, Alexander G, Mack, John, May, Aviwe K, Nyokong, Tebello, Gorbunova, Yulia G, Tsivadze, Aslan Yu
- Authors: Martynov, Alexander G , Mack, John , May, Aviwe K , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186915 , vital:44547 , xlink:href="https://doi.org/10.1021/acsomega.8b03500"
- Description: A methodological survey of density functional theory (DFT) methods for the prediction of UV−visible (vis)−near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm−Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV−visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAMB3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higherenergy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2−3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV−vis−NIR spectra of phthalocyanines and related macrocycles in the years ahead.
- Full Text:
- Date Issued: 2019
- Authors: Martynov, Alexander G , Mack, John , May, Aviwe K , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186915 , vital:44547 , xlink:href="https://doi.org/10.1021/acsomega.8b03500"
- Description: A methodological survey of density functional theory (DFT) methods for the prediction of UV−visible (vis)−near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm−Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV−visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAMB3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higherenergy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2−3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV−vis−NIR spectra of phthalocyanines and related macrocycles in the years ahead.
- Full Text:
- Date Issued: 2019
Methods for understanding social-ecological systems: a review of place-based studies
- de Vos, Alta, Biggs, Reinette, Preiser, Rika
- Authors: de Vos, Alta , Biggs, Reinette , Preiser, Rika
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/415909 , vital:71299 , xlink:href="https://doi.org/10.5751/ES-11236-240416"
- Description: In recent years, social-ecological systems (SES) have emerged as a prominent analytical framing with which to investigate pressing sustainability issues associated with the Anthropocene era. Despite the growth of SES research, the lack of a delineated set of methods commonly contributes to disorientation for those entering into a field where methodological pluralism is the norm. We conduct a review of SES research, focusing particularly on methods used in this field. Our results reflect the rapid growth in SES research relative to other publications in relevant subject areas, and suggest a maturation of the field. Whilst institutions investigating SES have been mostly based in the global north, focal SES has been more globally distributed, although key regions, especially island regions, remain poorly studied. Key problems addressed in the studies related to policy, trade, conservation, adaptation, land use change, water, forests, sustainability, urban problems, and governance and institutions. We identified 311 methods, which we grouped into 27 method categories that can serve as a guide to SES research methods for newcomers to the field. We also performed an exploratory assessment of the ability of these methods to account for key features of SES as complex adaptive systems. We found that methods do better at accounting for the relational and context-dependent nature of SES, and least well with complex causality. Our study highlights the plurality of methods used in SES research, and helps highlight key areas in need of further methodological development.
- Full Text:
- Date Issued: 2019
- Authors: de Vos, Alta , Biggs, Reinette , Preiser, Rika
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/415909 , vital:71299 , xlink:href="https://doi.org/10.5751/ES-11236-240416"
- Description: In recent years, social-ecological systems (SES) have emerged as a prominent analytical framing with which to investigate pressing sustainability issues associated with the Anthropocene era. Despite the growth of SES research, the lack of a delineated set of methods commonly contributes to disorientation for those entering into a field where methodological pluralism is the norm. We conduct a review of SES research, focusing particularly on methods used in this field. Our results reflect the rapid growth in SES research relative to other publications in relevant subject areas, and suggest a maturation of the field. Whilst institutions investigating SES have been mostly based in the global north, focal SES has been more globally distributed, although key regions, especially island regions, remain poorly studied. Key problems addressed in the studies related to policy, trade, conservation, adaptation, land use change, water, forests, sustainability, urban problems, and governance and institutions. We identified 311 methods, which we grouped into 27 method categories that can serve as a guide to SES research methods for newcomers to the field. We also performed an exploratory assessment of the ability of these methods to account for key features of SES as complex adaptive systems. We found that methods do better at accounting for the relational and context-dependent nature of SES, and least well with complex causality. Our study highlights the plurality of methods used in SES research, and helps highlight key areas in need of further methodological development.
- Full Text:
- Date Issued: 2019
Microbial agents for control of aquatic weeds and their role in integrated management
- Authors: Ray, P , Hill, Martin P
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/423550 , vital:72071 , xlink:href="https://www.cabidigitallibrary.org/doi/abs/10.1079/PAVSNNR20128014"
- Description: Aquatic ecosystems throughout the world are threatened by the presence of invasive aquatic plants, both floating and submerged. Some of the aquatic species, such as water hyacinth (Eichhornia crassipes [Mart.] Solms), alligator weed, Alternanthera philoxeroides (Mart.), giant salvinia, Salvinia molesta D.S. Mitchell and water lettuce (Pistia stratiotes L.), Griseb. despite being relatively minor problems in their native range, have become major invaders of aquatic habitats in other parts of the world after having escaped from their natural enemies. Unchecked growth of aquatic vegetation is generally undesirable and reduces the value of the water resource. Despite adopting all control options including manual, mechanical, chemical and classical biological, the problem persists. The current weed management is oriented towards finding approaches that are effective in controlling the weed and reducing environmental contamination from herbicides. Plant pathogens have been gaining increasing attention and interest among those concerned with developing environmentally friendly, effective and compatible approaches for integrated management of the noxious weeds. This paper discusses some of the major microbial agents associated with aquatic weeds and their increasing role in integrated weed management.
- Full Text:
- Date Issued: 2013
- Authors: Ray, P , Hill, Martin P
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/423550 , vital:72071 , xlink:href="https://www.cabidigitallibrary.org/doi/abs/10.1079/PAVSNNR20128014"
- Description: Aquatic ecosystems throughout the world are threatened by the presence of invasive aquatic plants, both floating and submerged. Some of the aquatic species, such as water hyacinth (Eichhornia crassipes [Mart.] Solms), alligator weed, Alternanthera philoxeroides (Mart.), giant salvinia, Salvinia molesta D.S. Mitchell and water lettuce (Pistia stratiotes L.), Griseb. despite being relatively minor problems in their native range, have become major invaders of aquatic habitats in other parts of the world after having escaped from their natural enemies. Unchecked growth of aquatic vegetation is generally undesirable and reduces the value of the water resource. Despite adopting all control options including manual, mechanical, chemical and classical biological, the problem persists. The current weed management is oriented towards finding approaches that are effective in controlling the weed and reducing environmental contamination from herbicides. Plant pathogens have been gaining increasing attention and interest among those concerned with developing environmentally friendly, effective and compatible approaches for integrated management of the noxious weeds. This paper discusses some of the major microbial agents associated with aquatic weeds and their increasing role in integrated weed management.
- Full Text:
- Date Issued: 2013
Microelectrochemical patterning of gold surfaces using 4-azidobenzenediazonium and scanning electrochemical microscopy
- Coates, Megan, Cabet, Eva, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Coates, Megan , Cabet, Eva , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247926 , vital:51630 , xlink:href="https://doi.org/10.1016/j.elecom.2010.11.037"
- Description: This work describes for the first time the possibility of performing local micro electrochemical grafting of a gold substrate by 4-azidobenzenediazonium by SECM in a single and simple one step without complications from adsorption. The electrografted spots of diazonium were performed by positioning a Pt tip at a given distance above the gold substrate and the SECM was used in a three-electrode configuration (the Pt tip serving as the microanode) in acetonitrile containing 5 mM 4-azidobenzenediazonium and 0.1 M Bu4NBF4 during 10 ms. The dimensions of the derivatized areas of the substrates were finely tuned by using different experimental conditions (tip distance above the substrate, tip diameter, presence or absence of supporting electrolyte). The use of the azido-derivated diazonium molecule and these preliminary results open the gate to important applications and developments devoted to the local micro functionalization of electrodes by thin layers that allow the implementation of the emerging and attractive interfacial click reaction.
- Full Text:
- Date Issued: 2011
- Authors: Coates, Megan , Cabet, Eva , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247926 , vital:51630 , xlink:href="https://doi.org/10.1016/j.elecom.2010.11.037"
- Description: This work describes for the first time the possibility of performing local micro electrochemical grafting of a gold substrate by 4-azidobenzenediazonium by SECM in a single and simple one step without complications from adsorption. The electrografted spots of diazonium were performed by positioning a Pt tip at a given distance above the gold substrate and the SECM was used in a three-electrode configuration (the Pt tip serving as the microanode) in acetonitrile containing 5 mM 4-azidobenzenediazonium and 0.1 M Bu4NBF4 during 10 ms. The dimensions of the derivatized areas of the substrates were finely tuned by using different experimental conditions (tip distance above the substrate, tip diameter, presence or absence of supporting electrolyte). The use of the azido-derivated diazonium molecule and these preliminary results open the gate to important applications and developments devoted to the local micro functionalization of electrodes by thin layers that allow the implementation of the emerging and attractive interfacial click reaction.
- Full Text:
- Date Issued: 2011
Microwave synthesis and photophysics of new tetrasulfonated tin (II) macrocycles
- Khene, Samson, Ogunsipe, Abimbola, Antunes, Edith M, Nyokong, Tebello
- Authors: Khene, Samson , Ogunsipe, Abimbola , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281269 , vital:55708 , xlink:href="https://doi.org/10.1142/S108842460700014X"
- Description: This work reports on the microwave synthesis of tetrasulfonated tin phthalocyanine and tetrasulfonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (more than 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The α,β,γ-tetrabenzcorrole complex has lower triplet life times and yields, while the binding constant and quenching (of bovine serum albumin) constant are lower for α,β,γ-tetrabenzcorrole compared to tetrasulfonated tin phthalocyanine.
- Full Text:
- Date Issued: 2007
- Authors: Khene, Samson , Ogunsipe, Abimbola , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281269 , vital:55708 , xlink:href="https://doi.org/10.1142/S108842460700014X"
- Description: This work reports on the microwave synthesis of tetrasulfonated tin phthalocyanine and tetrasulfonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (more than 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The α,β,γ-tetrabenzcorrole complex has lower triplet life times and yields, while the binding constant and quenching (of bovine serum albumin) constant are lower for α,β,γ-tetrabenzcorrole compared to tetrasulfonated tin phthalocyanine.
- Full Text:
- Date Issued: 2007
Miscellaneous provisions
- Arendse, Jacqueline A, Clegg, David, Williams, Robert C
- Authors: Arendse, Jacqueline A , Clegg, David , Williams, Robert C
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , book chapter
- Identifier: http://hdl.handle.net/10962/131276 , vital:36548 , https://store.lexisnexis.co.za/products/silke-on-tax-administration-skuZASKUPG1440
- Description: Miscellaneous provisions pertaining to tax administration are explained in this chapter.
- Full Text: false
- Date Issued: 2016
- Authors: Arendse, Jacqueline A , Clegg, David , Williams, Robert C
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , book chapter
- Identifier: http://hdl.handle.net/10962/131276 , vital:36548 , https://store.lexisnexis.co.za/products/silke-on-tax-administration-skuZASKUPG1440
- Description: Miscellaneous provisions pertaining to tax administration are explained in this chapter.
- Full Text: false
- Date Issued: 2016
Modelling dialectical processes in environmental learning
- Authors: Schudel, Ingrid J
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/294409 , vital:57219 , xlink:href="https://doi.org/10.1080/14767430.2017.1288061"
- Description: This paper describes a critical realist intensive case study, which develops and tests a ‘dialectic process model of transformative learning’. The model is inspired by Bhaskar's (1993) onto-axiological chain (or MELD Schema) as outlined in his formulation of dialectical critical realism. The study describes transformative environmental learning processes focusing on food security in two primary schools in rural South Africa. The model elaborates on the four links in the onto-axiological chain by describing four knowledge interests across the two cases: knowledge of ‘what is and what is not’, knowledge of ‘what could be’, knowledge of ‘what should be’, and knowledge of ‘what can be’. The model also highlights the emergent nature of epistemic relations in transformative learning processes. The paper discusses the model in relation to a transformative, open-ended and context specific approach to Environmental Education (EE)/ESD. The paper illustrates that Bhaskar’s MELD is a robust schema for investigating learning-led change in EE and suggests its relevance in other research contexts concerned with societal transformation.
- Full Text:
- Date Issued: 2017
- Authors: Schudel, Ingrid J
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/294409 , vital:57219 , xlink:href="https://doi.org/10.1080/14767430.2017.1288061"
- Description: This paper describes a critical realist intensive case study, which develops and tests a ‘dialectic process model of transformative learning’. The model is inspired by Bhaskar's (1993) onto-axiological chain (or MELD Schema) as outlined in his formulation of dialectical critical realism. The study describes transformative environmental learning processes focusing on food security in two primary schools in rural South Africa. The model elaborates on the four links in the onto-axiological chain by describing four knowledge interests across the two cases: knowledge of ‘what is and what is not’, knowledge of ‘what could be’, knowledge of ‘what should be’, and knowledge of ‘what can be’. The model also highlights the emergent nature of epistemic relations in transformative learning processes. The paper discusses the model in relation to a transformative, open-ended and context specific approach to Environmental Education (EE)/ESD. The paper illustrates that Bhaskar’s MELD is a robust schema for investigating learning-led change in EE and suggests its relevance in other research contexts concerned with societal transformation.
- Full Text:
- Date Issued: 2017
Modelling stock return volatility dynamics in selected African markets
- Authors: King, Daniel , Botha, Ferdi
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/396104 , vital:69150 , xlink:href=" https://doi.org/10.1016/j.econmod.2014.11.008"
- Description: This paper examines whether accounting for structural changes in the conditional variance process, through the use of Markov-switching models, improves estimates and forecasts of stock return volatility over those of the more conventional single-state (G)ARCH models, within and across selected African markets for the period 2002–2012. In the univariate portion of the paper, the performances of various Markov-switching models are tested against a single-state benchmark model through the use of in-sample goodness-of-fit and predictive ability measures. In the multivariate context, the single-state and Markov-switching models are comparatively assessed according to their usefulness in constructing optimal stock portfolios. Accounting for structural breaks in the conditional variance process, conventional GARCH effects remain important in capturing heteroscedasticity. However, those univariate models including a GARCH term perform comparatively poorly when used for forecasting purposes. In the multivariate study, the use of Markov-switching variance–covariance estimates improves risk-adjusted portfolio returns relative to portfolios constructed using the more conventional single-state models. While there is evidence that some Markov-switching models can provide better forecasts and higher risk-adjusted returns than those models which include GARCH effects, the inability of the simpler Markov-switching models to fully capture heteroscedasticity in the data remains problematic.
- Full Text:
- Date Issued: 2015
- Authors: King, Daniel , Botha, Ferdi
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/396104 , vital:69150 , xlink:href=" https://doi.org/10.1016/j.econmod.2014.11.008"
- Description: This paper examines whether accounting for structural changes in the conditional variance process, through the use of Markov-switching models, improves estimates and forecasts of stock return volatility over those of the more conventional single-state (G)ARCH models, within and across selected African markets for the period 2002–2012. In the univariate portion of the paper, the performances of various Markov-switching models are tested against a single-state benchmark model through the use of in-sample goodness-of-fit and predictive ability measures. In the multivariate context, the single-state and Markov-switching models are comparatively assessed according to their usefulness in constructing optimal stock portfolios. Accounting for structural breaks in the conditional variance process, conventional GARCH effects remain important in capturing heteroscedasticity. However, those univariate models including a GARCH term perform comparatively poorly when used for forecasting purposes. In the multivariate study, the use of Markov-switching variance–covariance estimates improves risk-adjusted portfolio returns relative to portfolios constructed using the more conventional single-state models. While there is evidence that some Markov-switching models can provide better forecasts and higher risk-adjusted returns than those models which include GARCH effects, the inability of the simpler Markov-switching models to fully capture heteroscedasticity in the data remains problematic.
- Full Text:
- Date Issued: 2015