Oxovanadium (IV)-catalysed oxidation of dibenzothiophene and 4, 6-dimethyldibenzothiophene
- Ogunlaja, Adeniyi S, Chidawanyika, Wadzanai J U, Antunes, Edith M, Fernandes, Manuel A, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Ogunlaja, Adeniyi S , Chidawanyika, Wadzanai J U , Antunes, Edith M , Fernandes, Manuel A , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246025 , vital:51429 , xlink:href="https://doi.org/10.1039/C2DT31433A"
- Description: The reaction between [VIVOSO4] and the tetradentate N2O2-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [VIVO(sal-HBPD)]. The molecular structure of [VIVO(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N2O2 binding mode of the tetradentate ligand. The formation of the polymer-supported p[VIVO(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [VIVOSO4]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[VIVO(sal-AHBPD)] were found to be 6.9 m2 g−1 and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[VIVO(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application of this catalyst in the oxidative desulfurization of crude oils.
- Full Text:
- Authors: Ogunlaja, Adeniyi S , Chidawanyika, Wadzanai J U , Antunes, Edith M , Fernandes, Manuel A , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246025 , vital:51429 , xlink:href="https://doi.org/10.1039/C2DT31433A"
- Description: The reaction between [VIVOSO4] and the tetradentate N2O2-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [VIVO(sal-HBPD)]. The molecular structure of [VIVO(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N2O2 binding mode of the tetradentate ligand. The formation of the polymer-supported p[VIVO(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [VIVOSO4]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[VIVO(sal-AHBPD)] were found to be 6.9 m2 g−1 and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[VIVO(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application of this catalyst in the oxidative desulfurization of crude oils.
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Part II Zef/poor white kitsch chique
- Authors: Krueger, Anton
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/225745 , vital:49255 , xlink:href="https://doi.org/10.1080/17533171.2012.715484"
- Description: Ninja, who fronts the freak hip-hop band Die Antwoord, might not be quite what Desmond Tutu had in mind when he described South Africans as the “Rainbow People of God,”24 a happy harmonious amalgamation of different races. In his introduction to their seminal comic track “Enter the Ninja,” Ninja presents himself, rather, as a mongrel gutter dog, both embracing and parodying a syncretic fusion of the many different cultures and races of South Africa, celebrating as well as subverting the rainbow nation discourse. As he said in an interview with News24: “South African culture is quite a fucking fruit salad … a fucking fucked rainbow nation. South Africa's totally fucked … but in a cool way.”25 The cool side of being “fucked” in this way is “Zef.” Zef denotes a particular style of vulgar humor (in the usual sense of the word “vulgar,” but also with a nod to its origin in the Latin vulgaris for “mob” or “commoners”), which has been emerging more and more in South Africa during the past decade. It involves a way of presenting a persona in a purposefully degrading way, exaggerating one's appearance and mannerisms as low class, ill bred, and boorish. I would like to consider the recent popularity of “Zef” and examine its connection specifically to popular Afrikaans folk rock culture, a lineage of white poverty, and the feeling of disgrace experienced by many white Afrikaners after the end of apartheid.
- Full Text:
- Authors: Krueger, Anton
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/225745 , vital:49255 , xlink:href="https://doi.org/10.1080/17533171.2012.715484"
- Description: Ninja, who fronts the freak hip-hop band Die Antwoord, might not be quite what Desmond Tutu had in mind when he described South Africans as the “Rainbow People of God,”24 a happy harmonious amalgamation of different races. In his introduction to their seminal comic track “Enter the Ninja,” Ninja presents himself, rather, as a mongrel gutter dog, both embracing and parodying a syncretic fusion of the many different cultures and races of South Africa, celebrating as well as subverting the rainbow nation discourse. As he said in an interview with News24: “South African culture is quite a fucking fruit salad … a fucking fucked rainbow nation. South Africa's totally fucked … but in a cool way.”25 The cool side of being “fucked” in this way is “Zef.” Zef denotes a particular style of vulgar humor (in the usual sense of the word “vulgar,” but also with a nod to its origin in the Latin vulgaris for “mob” or “commoners”), which has been emerging more and more in South Africa during the past decade. It involves a way of presenting a persona in a purposefully degrading way, exaggerating one's appearance and mannerisms as low class, ill bred, and boorish. I would like to consider the recent popularity of “Zef” and examine its connection specifically to popular Afrikaans folk rock culture, a lineage of white poverty, and the feeling of disgrace experienced by many white Afrikaners after the end of apartheid.
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The photophysical and energy transfer behaviour of low symmetry phthalocyanine complexes conjugated to coreshell quantum dots
- Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243051 , vital:51111 , xlink:href="https://doi.org/10.1016/j.jphotochem.2012.07.016"
- Description: This work reports on the synthesis of new coreshell quantum dots (QDs)-low symmetry phthalocyanines conjugates. The energy transfer from QDs (donor) to phthalocyanines (acceptor) was investigated when the two are mixed together or chemically linked to each other. Ti monocarboxy phthalocyanine QDs-linked and Sn monocarboxy phthalocyanine QDs-linked gave the smallest centre-to-centre separation distance (r) corresponding to their higher Förster resonance energy transfer efficiencies which are estimated at 0.76 and 0.85 respectively. Higher energy transfer behaviour was achieved for all the covalently linked conjugates compared to their corresponding mixed counterparts. An improvement in triplet quantum yields and lifetimes was achieved for all the complexes in the presence of quantum dots, with the linked counterparts displaying excellent triplet state behaviour.
- Full Text:
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243051 , vital:51111 , xlink:href="https://doi.org/10.1016/j.jphotochem.2012.07.016"
- Description: This work reports on the synthesis of new coreshell quantum dots (QDs)-low symmetry phthalocyanines conjugates. The energy transfer from QDs (donor) to phthalocyanines (acceptor) was investigated when the two are mixed together or chemically linked to each other. Ti monocarboxy phthalocyanine QDs-linked and Sn monocarboxy phthalocyanine QDs-linked gave the smallest centre-to-centre separation distance (r) corresponding to their higher Förster resonance energy transfer efficiencies which are estimated at 0.76 and 0.85 respectively. Higher energy transfer behaviour was achieved for all the covalently linked conjugates compared to their corresponding mixed counterparts. An improvement in triplet quantum yields and lifetimes was achieved for all the complexes in the presence of quantum dots, with the linked counterparts displaying excellent triplet state behaviour.
- Full Text:
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