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:
- Date Issued: 2012
- 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:
- Date Issued: 2012
Photooxidation of 4-chlorophenol sensitized by lutetium tetraphenoxy phthalocyanine anchored on electrospun polystyrene polymer fiber
- Zugle, Ruphino, Antunes, Edith M, Khene, Samson M, Nyokong, Tebello
- Authors: Zugle, Ruphino , Antunes, Edith M , Khene, Samson M , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245787 , vital:51405 , xlink:href="https://doi.org/10.1016/j.poly.2011.11.005"
- Description: An electrospun polystyrene (PS) fiber incorporating tetraphenoxy phthalocyanine complex of lutetium (LuTPPc/PS) as a photosensitizer was applied for the degradation of 4-chlorophenol in aqueous solution in the presence of visible light. The photocatalytic activity of the LuTPPc in the fiber was compared to that of zinc phthalocyanine (ZnPc) incorporated into the PS fiber, and the former showed higher activity. UV–Vis spectral changes of sample solutions indicated transformation of the analyte with first order kinetics and half-lives that are within one and half hours for LuTPPc/PS. Products identified from the spectral changes and gas chromatography were benzoquinone, hydroquinone and 4,4′-dihydroxydiphenol suggesting that the photodegradation of 4-chlorophenol was through both Types I and II mechanisms.
- Full Text:
- Date Issued: 2012
- Authors: Zugle, Ruphino , Antunes, Edith M , Khene, Samson M , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245787 , vital:51405 , xlink:href="https://doi.org/10.1016/j.poly.2011.11.005"
- Description: An electrospun polystyrene (PS) fiber incorporating tetraphenoxy phthalocyanine complex of lutetium (LuTPPc/PS) as a photosensitizer was applied for the degradation of 4-chlorophenol in aqueous solution in the presence of visible light. The photocatalytic activity of the LuTPPc in the fiber was compared to that of zinc phthalocyanine (ZnPc) incorporated into the PS fiber, and the former showed higher activity. UV–Vis spectral changes of sample solutions indicated transformation of the analyte with first order kinetics and half-lives that are within one and half hours for LuTPPc/PS. Products identified from the spectral changes and gas chromatography were benzoquinone, hydroquinone and 4,4′-dihydroxydiphenol suggesting that the photodegradation of 4-chlorophenol was through both Types I and II mechanisms.
- Full Text:
- Date Issued: 2012
Synthesis and photophysical behavior of a novel zinc phthalocyanine containing a single carboxylic acid and three phenylthio substituents
- Forteath, Shaun, Antunes, Edith M, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243207 , vital:51127 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.03.050"
- Description: Zinc 2, (3)-tri-(phenylthio)-2, (3)-carboxy phthalocyanine (ZnPc(COOH)(SPh)3), zinc 2, (3)-tetra-(phenylthio) phthalocyanine (ZnPc(SPh)4) and 2, (3)-tetra-(phenylthio) phthalocyanine (H2Pc(SPh)4) were synthesized and their photophysical behavior were compared with those of a number of zinc phthalocyanine (ZnPc) derivatives. ZnPc(COOH)(SPh)3 and ZnPc(SPh)4 had similar fluorescence (ΦF=0.14) and triplet state (ΦT=0.65) quantum yields in dimethylsulfoxide, hence showing no effects of the replacement of one of the phenylthio groups with a carboxylic acid group. ZnPc(COOH)(SPh)3 displayed a slightly shorter triplet lifetime (τT=331 μs) than ZnPc (τT=350 μs) in DMSO, but within the range of ZnPc derivatives. The triplet lifetime for ZnPc(COOH)(SPh)3 is much longer than for the symmetrical derivative (ZnPc(SPh)4) with τT=149 μs in DMSO.
- Full Text:
- Date Issued: 2012
- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243207 , vital:51127 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.03.050"
- Description: Zinc 2, (3)-tri-(phenylthio)-2, (3)-carboxy phthalocyanine (ZnPc(COOH)(SPh)3), zinc 2, (3)-tetra-(phenylthio) phthalocyanine (ZnPc(SPh)4) and 2, (3)-tetra-(phenylthio) phthalocyanine (H2Pc(SPh)4) were synthesized and their photophysical behavior were compared with those of a number of zinc phthalocyanine (ZnPc) derivatives. ZnPc(COOH)(SPh)3 and ZnPc(SPh)4 had similar fluorescence (ΦF=0.14) and triplet state (ΦT=0.65) quantum yields in dimethylsulfoxide, hence showing no effects of the replacement of one of the phenylthio groups with a carboxylic acid group. ZnPc(COOH)(SPh)3 displayed a slightly shorter triplet lifetime (τT=331 μs) than ZnPc (τT=350 μs) in DMSO, but within the range of ZnPc derivatives. The triplet lifetime for ZnPc(COOH)(SPh)3 is much longer than for the symmetrical derivative (ZnPc(SPh)4) with τT=149 μs in DMSO.
- Full Text:
- Date Issued: 2012
Synthesis and photophysicochemical properties of novel zinc phthalocyanines mono substituted with carboxyl containing functional groups
- Rapulenyane, Nomasonto, Antunes, Edith M, Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Rapulenyane, Nomasonto , Antunes, Edith M , Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242389 , vital:51037 , xlink:href="https://doi.org/10.1016/j.jphotochem.2012.09.007"
- Description: This work reports on the synthesis and the physicochemical properties of novel unsymmetrically substituted zinc phthalocyanines (complexes 8, 10 and 11) and their symmetrically substituted counterparts (complexes 9, 12 and 13). The new complexes and their counterparts were successfully structurally characterized by IR, NMR, mass spectral and elemental analyses. Low fluorescence quantum yields (0.032) and lifetimes (0.91 ns) were obtained for the symmetrical ZnOTPc (complex 9) compared to the higher fluorescence quantum yields (0.15, 0.13, 0.10, 0.09 and 0.29) and lifetimes (4.4, 1.69, 1.69, 2.16 and 3.23 ns) obtained for ZnMPCPc (8), ZnTDTPc (12), ZnMCapPc (10), ZnMCafPc (11) and ZnTCPPc (13), respectively. All the complexes showed the ability to produce singlet oxygen with the highest triplet quantum yields obtained for 8 and 10 (0.80 and 0.65 respectively). High triplet lifetimes (109–286 μs) were obtained for all complexes. Complex 8 showed the longest triplet and fluorescence lifetimes as well the largest triplet state and singlet oxygen quantum yields.
- Full Text:
- Date Issued: 2012
- Authors: Rapulenyane, Nomasonto , Antunes, Edith M , Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242389 , vital:51037 , xlink:href="https://doi.org/10.1016/j.jphotochem.2012.09.007"
- Description: This work reports on the synthesis and the physicochemical properties of novel unsymmetrically substituted zinc phthalocyanines (complexes 8, 10 and 11) and their symmetrically substituted counterparts (complexes 9, 12 and 13). The new complexes and their counterparts were successfully structurally characterized by IR, NMR, mass spectral and elemental analyses. Low fluorescence quantum yields (0.032) and lifetimes (0.91 ns) were obtained for the symmetrical ZnOTPc (complex 9) compared to the higher fluorescence quantum yields (0.15, 0.13, 0.10, 0.09 and 0.29) and lifetimes (4.4, 1.69, 1.69, 2.16 and 3.23 ns) obtained for ZnMPCPc (8), ZnTDTPc (12), ZnMCapPc (10), ZnMCafPc (11) and ZnTCPPc (13), respectively. All the complexes showed the ability to produce singlet oxygen with the highest triplet quantum yields obtained for 8 and 10 (0.80 and 0.65 respectively). High triplet lifetimes (109–286 μs) were obtained for all complexes. Complex 8 showed the longest triplet and fluorescence lifetimes as well the largest triplet state and singlet oxygen quantum yields.
- Full Text:
- Date Issued: 2012
Synthesis and physicochemical behaviour of aluminium trikis and tetrakis (diaquaplatinum) octacarboxyphthalocynine
- Malinga, Nduduzo, Dolotova, Olga V, Bulgakov, Roman, Antunes, Edith M, Nyokong, Tebello
- Authors: Malinga, Nduduzo , Dolotova, Olga V , Bulgakov, Roman , Antunes, Edith M , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242687 , vital:51068 , xlink:href="https://doi.org/10.1016/j.dyepig.2012.05.011"
- Description: The combination of chemotherapy and photodynamic therapy was investigated by the synthesis and characterisation of phthalocyanine conjugates with Pt complexes. The complexes synthesized are: hydroxoaluminum trikis(diaquaplatinum) octacarboxyphthalocyanine (OHAlOCPc(Pt)3) and hydroxoaluminum tetrakis(diaquaplatinum) octacarboxyphthalocyanine (OHAlOCPc(Pt)4). The platinated phthalocyanine complexes gave long triplet lifetimes of 577 and 526 μs for OHAlOCPc(Pt)3 and OHAlOCPc(Pt)4, respectively. The triplet quantum yields were found to be 0.45 for OHAlOCPc(Pt)3 and 0.57 OHAlOCPc(Pt)4 while the singlet oxygen quantum yields were found to be 0.38 and 0.48, respectively.
- Full Text:
- Date Issued: 2012
- Authors: Malinga, Nduduzo , Dolotova, Olga V , Bulgakov, Roman , Antunes, Edith M , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242687 , vital:51068 , xlink:href="https://doi.org/10.1016/j.dyepig.2012.05.011"
- Description: The combination of chemotherapy and photodynamic therapy was investigated by the synthesis and characterisation of phthalocyanine conjugates with Pt complexes. The complexes synthesized are: hydroxoaluminum trikis(diaquaplatinum) octacarboxyphthalocyanine (OHAlOCPc(Pt)3) and hydroxoaluminum tetrakis(diaquaplatinum) octacarboxyphthalocyanine (OHAlOCPc(Pt)4). The platinated phthalocyanine complexes gave long triplet lifetimes of 577 and 526 μs for OHAlOCPc(Pt)3 and OHAlOCPc(Pt)4, respectively. The triplet quantum yields were found to be 0.45 for OHAlOCPc(Pt)3 and 0.57 OHAlOCPc(Pt)4 while the singlet oxygen quantum yields were found to be 0.38 and 0.48, respectively.
- Full Text:
- Date Issued: 2012
Synthesis of phthalocyanine conjugates with gold nanoparticles and liposomes for photodynamic therapy
- Nombona, Nolwazi, Maduray, Kaminee, Antunes, Edith M, Karsten, Aletta, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Maduray, Kaminee , Antunes, Edith M , Karsten, Aletta , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245798 , vital:51406 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2011.11.007"
- Description: The efficiency of [2,9,17,23-tetrakis-(1,6-hexanedithiol)phthalocyaninato]zinc(II) as a photodynamic therapy (PDT) agent was investigated. This compound belongs to the second generation of photosensitizers currently tested for the cellular photo-damage of cancer cells. The production of reactive oxygen species (ROS) and phototoxicity of the photosensitizer were assessed. Healthy fibroblast cells and breast cancer (MCF-7) cells were treated with either free phthalocyanine or phthalocyanine bound to either gold nanoparticles or encapsulated in liposomes. Cell viability studies showed the optimum phototoxic effect on non-malignant cells to be 4.5 J cm−2. The PDT effect of the liposome bound phthalocyanine showed extensive damage of the breast cancer cells. Gold nanoparticles only showed a modest improvement in PDT activity.
- Full Text:
- Date Issued: 2012
- Authors: Nombona, Nolwazi , Maduray, Kaminee , Antunes, Edith M , Karsten, Aletta , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245798 , vital:51406 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2011.11.007"
- Description: The efficiency of [2,9,17,23-tetrakis-(1,6-hexanedithiol)phthalocyaninato]zinc(II) as a photodynamic therapy (PDT) agent was investigated. This compound belongs to the second generation of photosensitizers currently tested for the cellular photo-damage of cancer cells. The production of reactive oxygen species (ROS) and phototoxicity of the photosensitizer were assessed. Healthy fibroblast cells and breast cancer (MCF-7) cells were treated with either free phthalocyanine or phthalocyanine bound to either gold nanoparticles or encapsulated in liposomes. Cell viability studies showed the optimum phototoxic effect on non-malignant cells to be 4.5 J cm−2. The PDT effect of the liposome bound phthalocyanine showed extensive damage of the breast cancer cells. Gold nanoparticles only showed a modest improvement in PDT activity.
- Full Text:
- Date Issued: 2012
Unquenched fluorescence lifetime for β-phenylthio substituted zinc phthalocyanine upon conjugation to gold nanoparticles
- Forteath, Shaun, Antunes, Edith M, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245774 , vital:51404 , xlink:href="https://doi.org/10.1016/j.poly.2011.12.015"
- Description: Photoinduced processes in phthalocyanine-functionalized gold nanoparticles have been investigated by spectroscopic measurements. The zinc phthalocyanine used contained four phenylthio peripheral substituents (ZnPc(SPh)4). The conjugates formed are represented as ZnPc(SPh)4–AuNP. The absorption spectrum of the ZnPc(SPh)4–AuNP shows a broadening of the phthalocyanine Q-band absorption, probably due to a tight packing of the phthalocyanines on the gold nanoparticle surface. For the attached phthalocyanines, the two fluorescence lifetimes obtained by time-correlated single photon counting (TCSPC) were determined to be both longer and shorter than that of the free Pc. The fluorescence lifetimes were resolved using time resolved fluorescence spectroscopy (TRES).
- Full Text:
- Date Issued: 2012
- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245774 , vital:51404 , xlink:href="https://doi.org/10.1016/j.poly.2011.12.015"
- Description: Photoinduced processes in phthalocyanine-functionalized gold nanoparticles have been investigated by spectroscopic measurements. The zinc phthalocyanine used contained four phenylthio peripheral substituents (ZnPc(SPh)4). The conjugates formed are represented as ZnPc(SPh)4–AuNP. The absorption spectrum of the ZnPc(SPh)4–AuNP shows a broadening of the phthalocyanine Q-band absorption, probably due to a tight packing of the phthalocyanines on the gold nanoparticle surface. For the attached phthalocyanines, the two fluorescence lifetimes obtained by time-correlated single photon counting (TCSPC) were determined to be both longer and shorter than that of the free Pc. The fluorescence lifetimes were resolved using time resolved fluorescence spectroscopy (TRES).
- Full Text:
- Date Issued: 2012
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