Imidazole-functionalized polymer microspheres and fibers–useful materials for immobilization of oxovanadium (IV) catalysts
- Walmsley, Ryan S, Ogunlaja, Adeniyi S, Coombes, Matthew J, Chidawanyika, Wadzanai J U, Litwinski, Christian, Torto, Nelson, Nyokong, Tebello, Tshentu, Zenixole R
- Authors: Walmsley, Ryan S , Ogunlaja, Adeniyi S , Coombes, Matthew J , Chidawanyika, Wadzanai J U , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246041 , vital:51431 , xlink:href="https://doi.org/10.1039/C2JM15485D"
- Description: Both polymer microspheres and microfibers containing the imidazole functionality have been prepared and used to immobilize oxovanadium(IV). The average diameters and BET surface areas of the microspheres were 322 μm and 155 m2 g−1 while the fibers were 1.85 μm and 52 m2 g−1, respectively. XPS and microanalysis confirmed the incorporation of imidazole and vanadium in the polymeric materials. The catalytic activity of both materials was evaluated using the hydrogen peroxide facilitated oxidation of thioanisole. The microspheres were applied in a typical laboratory batch reactor set-up and quantitative conversions (>99%) were obtained in under 240 min with turn-over frequencies ranging from 21.89 to 265.53 h−1, depending on the quantity of catalyst and temperature. The microspherical catalysts also proved to be recyclable with no drop in activity being observed after three successive reactions. The vanadium functionalized fibers were applied in a pseudo continuous flow set-up. Factors influencing the overall conversion and product selectivity, including flow rate and catalyst quantity, were investigated. At flow rates of 1–4 mL h−1 near quantitative conversion was maintained over an extended period. Keeping the mass of catalyst constant (0.025 g) and varying the flow rate from 1–6 mL h−1 resulted in a shift in the formation of the oxidation product methyl phenyl sulfone from 60.1 to 18.6%.
- Full Text:
- Date Issued: 2012
- Authors: Walmsley, Ryan S , Ogunlaja, Adeniyi S , Coombes, Matthew J , Chidawanyika, Wadzanai J U , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246041 , vital:51431 , xlink:href="https://doi.org/10.1039/C2JM15485D"
- Description: Both polymer microspheres and microfibers containing the imidazole functionality have been prepared and used to immobilize oxovanadium(IV). The average diameters and BET surface areas of the microspheres were 322 μm and 155 m2 g−1 while the fibers were 1.85 μm and 52 m2 g−1, respectively. XPS and microanalysis confirmed the incorporation of imidazole and vanadium in the polymeric materials. The catalytic activity of both materials was evaluated using the hydrogen peroxide facilitated oxidation of thioanisole. The microspheres were applied in a typical laboratory batch reactor set-up and quantitative conversions (>99%) were obtained in under 240 min with turn-over frequencies ranging from 21.89 to 265.53 h−1, depending on the quantity of catalyst and temperature. The microspherical catalysts also proved to be recyclable with no drop in activity being observed after three successive reactions. The vanadium functionalized fibers were applied in a pseudo continuous flow set-up. Factors influencing the overall conversion and product selectivity, including flow rate and catalyst quantity, were investigated. At flow rates of 1–4 mL h−1 near quantitative conversion was maintained over an extended period. Keeping the mass of catalyst constant (0.025 g) and varying the flow rate from 1–6 mL h−1 resulted in a shift in the formation of the oxidation product methyl phenyl sulfone from 60.1 to 18.6%.
- Full Text:
- Date Issued: 2012
In vitro photodynamic effect of aluminum tetrasulfophthalocyanines on melanoma skin cancer and healthy normal skin cells
- Maduray, Kaminee, Odhay, Bharti, Nyokong, Tebello
- Authors: Maduray, Kaminee , Odhay, Bharti , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245762 , vital:51403 , xlink:href="https://doi.org/10.1016/j.pdpdt.2011.07.001"
- Description: Photodynamic therapy is a medical treatment that uses an inactive dye/drug and lasers as a light source to activate the dye/drug to produce a toxic form of oxygen that destroys the cancer cells. This study aimed at investigating the cytotoxic effects of different concentrations of aluminum tetrasulfophthalocyanines in its inactive and active state (laser induced) on melanoma skin cancer cells, healthy normal skin fibroblast and keratinocyte cells. Experimentally, 3 x 10(4) cells/ml were seeded in 24-well plates before treatment with different concentrations of aluminum tetrasulfophthalocyanines. After 2 h, cells were irradiated with a light dose of 4.5 J/cm(2). Post-irradiated cells were incubated for 24 h before cell viability was measured using the CellTiter-Blue Viability Assay. Results showed that aluminum tetrasulfophthalocyanines at high concentrations were cytotoxic to melanoma cells in the absence of laser activation. In the presence of laser activation of aluminum tetrasulfophthalocyanines at a concentration of 40 mu g/ml decreased cell viability of melanoma cells to 45%, fibroblasts to 78% and keratinocytes to 73%. At this photosensitizing concentration of aluminum tetrasulfophthalocyanines the efficacy of the treatment light dose 4.5 J/cm(2) and the cell death mechanism induced by photoactivated aluminum tetrasulfophthalocyanines was evaluated. A light dose of 4.5 J/cm(2) was more efficient in killing a higher number of melanoma cells and a lower number of fibroblast and keratinocyte cells than the other light doses of 2.5 J/cm(2), 7.5 J/cm(2) and 10.5 J/cm(2). Apoptosis features such as blebbing, nucleus condensation, nucleus fragmentation and the formation of apoptotic bodies were seen in the photodynamic therapy treated melanoma skin cancer cells. This in vitro photodynamic therapy study concludes that using aluminum tetrasulfophthalocyanines at a photosensitizing concentration of 40 mu g/ml in combination with a laser dose of 4.5 J/cm(2) was potentially lethal for melanoma skin cancer cells and less harmful for the normal healthy skin cells. (c) 2011 Elsevier B.V. All rights reserved.
- Full Text:
- Date Issued: 2012
- Authors: Maduray, Kaminee , Odhay, Bharti , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245762 , vital:51403 , xlink:href="https://doi.org/10.1016/j.pdpdt.2011.07.001"
- Description: Photodynamic therapy is a medical treatment that uses an inactive dye/drug and lasers as a light source to activate the dye/drug to produce a toxic form of oxygen that destroys the cancer cells. This study aimed at investigating the cytotoxic effects of different concentrations of aluminum tetrasulfophthalocyanines in its inactive and active state (laser induced) on melanoma skin cancer cells, healthy normal skin fibroblast and keratinocyte cells. Experimentally, 3 x 10(4) cells/ml were seeded in 24-well plates before treatment with different concentrations of aluminum tetrasulfophthalocyanines. After 2 h, cells were irradiated with a light dose of 4.5 J/cm(2). Post-irradiated cells were incubated for 24 h before cell viability was measured using the CellTiter-Blue Viability Assay. Results showed that aluminum tetrasulfophthalocyanines at high concentrations were cytotoxic to melanoma cells in the absence of laser activation. In the presence of laser activation of aluminum tetrasulfophthalocyanines at a concentration of 40 mu g/ml decreased cell viability of melanoma cells to 45%, fibroblasts to 78% and keratinocytes to 73%. At this photosensitizing concentration of aluminum tetrasulfophthalocyanines the efficacy of the treatment light dose 4.5 J/cm(2) and the cell death mechanism induced by photoactivated aluminum tetrasulfophthalocyanines was evaluated. A light dose of 4.5 J/cm(2) was more efficient in killing a higher number of melanoma cells and a lower number of fibroblast and keratinocyte cells than the other light doses of 2.5 J/cm(2), 7.5 J/cm(2) and 10.5 J/cm(2). Apoptosis features such as blebbing, nucleus condensation, nucleus fragmentation and the formation of apoptotic bodies were seen in the photodynamic therapy treated melanoma skin cancer cells. This in vitro photodynamic therapy study concludes that using aluminum tetrasulfophthalocyanines at a photosensitizing concentration of 40 mu g/ml in combination with a laser dose of 4.5 J/cm(2) was potentially lethal for melanoma skin cancer cells and less harmful for the normal healthy skin cells. (c) 2011 Elsevier B.V. All rights reserved.
- Full Text:
- Date Issued: 2012
Interaction of CdTe quantum dots with 2, 2-diphenyl-1-picrylhydrazyl free radical
- Adegoke, Oluwasesan, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245751 , vital:51402 , xlink:href="https://doi.org/10.1007/s10895-011-1012-2"
- Description: The interaction of 2,2-diphenyl-1-picrylhydrazyl (DPPH●) free radical with thiol-capped CdTe quantum dots (QDs) has been studied by UV–vis spectroscopy, steady state and time resolved fluorescence measurements. Addition of DPPH● radical to CdTe QDs resulted in fluorescence quenching. The interaction occurs through static quenching as this was confirmed by fluorescence lifetime measurements. Time course absorption studies indicates that DPPH● may be reduced by interaction with QDs to the substituted hydrazine form (2,2-diphenyl-1-picrylhydrazine) DPPH-H. The mechanism of fluorescence quenching of CdTe QDs by DPPH● is proposed.
- Full Text:
- Date Issued: 2012
- Authors: Adegoke, Oluwasesan , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245751 , vital:51402 , xlink:href="https://doi.org/10.1007/s10895-011-1012-2"
- Description: The interaction of 2,2-diphenyl-1-picrylhydrazyl (DPPH●) free radical with thiol-capped CdTe quantum dots (QDs) has been studied by UV–vis spectroscopy, steady state and time resolved fluorescence measurements. Addition of DPPH● radical to CdTe QDs resulted in fluorescence quenching. The interaction occurs through static quenching as this was confirmed by fluorescence lifetime measurements. Time course absorption studies indicates that DPPH● may be reduced by interaction with QDs to the substituted hydrazine form (2,2-diphenyl-1-picrylhydrazine) DPPH-H. The mechanism of fluorescence quenching of CdTe QDs by DPPH● is proposed.
- Full Text:
- Date Issued: 2012
Layer by Layer Electrode Surface Functionalisation Using Carbon Nanotubes, Electrochemical Grafting of Azide‐Alkyne Functions and Click Chemistry
- Coates, Megan, Griveau, Sophie, Bedioui, Fethi, Nyokong, Tebello
- Authors: Coates, Megan , Griveau, Sophie , Bedioui, Fethi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243509 , vital:51159 , xlink:href="https://doi.org/10.1002/elan.201200240"
- Description: Ferrocene was covalently bonded to a layer of adsorbed single-walled carbon nanotubes on a glassy carbon electrode surface using electrochemical grafting and click chemistry. Grafting of the 4-azidobenzenediazonium salt onto the surface was accomplished by electrochemical reduction. The surface-bound azide groups, with the use of a copper(I) catalyst, were reacted with ethynylferrocene to form covalent 1,2,3-triazole bonds by click chemistry. This layer by layer construction of the electrode surface results in stable electrodes by combining good electrical conductivity and increased surface area of the nanotubes with the versatility of the Sharpless click reaction.
- Full Text:
- Date Issued: 2012
- Authors: Coates, Megan , Griveau, Sophie , Bedioui, Fethi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243509 , vital:51159 , xlink:href="https://doi.org/10.1002/elan.201200240"
- Description: Ferrocene was covalently bonded to a layer of adsorbed single-walled carbon nanotubes on a glassy carbon electrode surface using electrochemical grafting and click chemistry. Grafting of the 4-azidobenzenediazonium salt onto the surface was accomplished by electrochemical reduction. The surface-bound azide groups, with the use of a copper(I) catalyst, were reacted with ethynylferrocene to form covalent 1,2,3-triazole bonds by click chemistry. This layer by layer construction of the electrode surface results in stable electrodes by combining good electrical conductivity and increased surface area of the nanotubes with the versatility of the Sharpless click reaction.
- Full Text:
- Date Issued: 2012
Like a bolt from the blue : phthalocyanines in biomedical optics
- Sekkat, N, Van den Berg, H, Nyokong, Tebello, Lange, N
- Authors: Sekkat, N , Van den Berg, H , Nyokong, Tebello , Lange, N
- Date: 2012
- Subjects: Biomedical optics Fluorescence diagnosis Phthalocyanines NIR dyes Photodynamic therapy
- Language: English
- Type: Article
- Identifier: vital:6597 , http://hdl.handle.net/10962/d1004346 , http://dx.doi.org/10.3390/molecules17010098
- Description: The purpose of this review is to compile preclinical and clinical results on phthalocyanines (Pcs) as photosensitizers (PS) for Photodynamic Therapy (PDT) and contrast agents for fluorescence imaging. Indeed, Pcs are excellent candidates in these fields due to their strong absorbance in the NIR region and high chemical and photo-stability. In particular, this is mostly relevant for their in vivo activation in deeper tissular regions. However, most Pcs present two major limitations, i.e., a strong tendency to aggregate and a low water-solubility. In order to overcome these issues, both chemical tuning and pharmaceutical formulation combined with tumor targeting strategies were applied. These aspects will be developed in this review for the most extensively studied Pcs during the last 25 years, i.e., aluminium-, zinc- and silicon-based Pcs.
- Full Text:
- Date Issued: 2012
- Authors: Sekkat, N , Van den Berg, H , Nyokong, Tebello , Lange, N
- Date: 2012
- Subjects: Biomedical optics Fluorescence diagnosis Phthalocyanines NIR dyes Photodynamic therapy
- Language: English
- Type: Article
- Identifier: vital:6597 , http://hdl.handle.net/10962/d1004346 , http://dx.doi.org/10.3390/molecules17010098
- Description: The purpose of this review is to compile preclinical and clinical results on phthalocyanines (Pcs) as photosensitizers (PS) for Photodynamic Therapy (PDT) and contrast agents for fluorescence imaging. Indeed, Pcs are excellent candidates in these fields due to their strong absorbance in the NIR region and high chemical and photo-stability. In particular, this is mostly relevant for their in vivo activation in deeper tissular regions. However, most Pcs present two major limitations, i.e., a strong tendency to aggregate and a low water-solubility. In order to overcome these issues, both chemical tuning and pharmaceutical formulation combined with tumor targeting strategies were applied. These aspects will be developed in this review for the most extensively studied Pcs during the last 25 years, i.e., aluminium-, zinc- and silicon-based Pcs.
- Full Text:
- Date Issued: 2012
Molecular catalysis of the oxygen reduction reaction by iron porphyrin catalysts tethered into Nafion layers
- He, Qinggang, Mugadza, Tawanda, Kang, Xiongwu, Zhu, Xiaobing, Chen, Shaowei, Kerr, John, Nyokong, Tebello
- Authors: He, Qinggang , Mugadza, Tawanda , Kang, Xiongwu , Zhu, Xiaobing , Chen, Shaowei , Kerr, John , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243168 , vital:51123 , xlink:href="https://doi.org/10.1016/j.jpowsour.2012.05.043"
- Description: This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nafion and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV–Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nafion ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion® 212 membrane, and a Fe(III)TMPyP + Nafion ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H2/O2 proton exchange membrane (PEM) fuel cell test.
- Full Text:
- Date Issued: 2012
- Authors: He, Qinggang , Mugadza, Tawanda , Kang, Xiongwu , Zhu, Xiaobing , Chen, Shaowei , Kerr, John , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243168 , vital:51123 , xlink:href="https://doi.org/10.1016/j.jpowsour.2012.05.043"
- Description: This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nafion and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV–Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nafion ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion® 212 membrane, and a Fe(III)TMPyP + Nafion ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H2/O2 proton exchange membrane (PEM) fuel cell test.
- Full Text:
- Date Issued: 2012
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
Photophysical and photochemical properties of novel phthalocyanines bearing non-peripherally substituted mercaptoquinoline moiety
- Yaşa, Göknur, Erdoğmuş, Ali, Uğur, Ahmet Lütf, Şener, M Kasım, Avcıata, Ulvi, Nyokong, Tebello
- Authors: Yaşa, Göknur , Erdoğmuş, Ali , Uğur, Ahmet Lütf , Şener, M Kasım , Avcıata, Ulvi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244360 , vital:51250 , xlink:href="https://doi.org/10.1142/S1088424612500940"
- Description: The synthesis, photophysical and photochemical properties of nonperipherally (a) mercaptoquinoline substituted Zn(II), TiO(IV) and Mg(II) and quaternized Zn(II) phthalocyanines are described for the first time. These complexes (2 to 5) and their precursor are characterized by elemental analysis, FT-IR, 1 H NMR, electronic spectroscopy as well as mass spectroscopy. Complexes 2, 4 and 5 have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated in all solvents within a wide concentration range. Complex 3 showed very good solubility in water as well as DMSO and DMF. General trends are described for singlet oxygen, photodegradation and fluorescence quantum yields of these complexes in DMSO and DMF. While complex 2 has higher singlet oxygen and fluorescence quantum yields than 3, 4 and 5, complex 4 has higher fluorescence quantum yields in DMF and DMSO than 2, 3 and 5. The effect of the solvents and metal on the photophysical and photochemical parameters of the metallophthalocyanines are also reported.
- Full Text:
- Date Issued: 2012
- Authors: Yaşa, Göknur , Erdoğmuş, Ali , Uğur, Ahmet Lütf , Şener, M Kasım , Avcıata, Ulvi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244360 , vital:51250 , xlink:href="https://doi.org/10.1142/S1088424612500940"
- Description: The synthesis, photophysical and photochemical properties of nonperipherally (a) mercaptoquinoline substituted Zn(II), TiO(IV) and Mg(II) and quaternized Zn(II) phthalocyanines are described for the first time. These complexes (2 to 5) and their precursor are characterized by elemental analysis, FT-IR, 1 H NMR, electronic spectroscopy as well as mass spectroscopy. Complexes 2, 4 and 5 have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated in all solvents within a wide concentration range. Complex 3 showed very good solubility in water as well as DMSO and DMF. General trends are described for singlet oxygen, photodegradation and fluorescence quantum yields of these complexes in DMSO and DMF. While complex 2 has higher singlet oxygen and fluorescence quantum yields than 3, 4 and 5, complex 4 has higher fluorescence quantum yields in DMF and DMSO than 2, 3 and 5. The effect of the solvents and metal on the photophysical and photochemical parameters of the metallophthalocyanines are also reported.
- Full Text:
- Date Issued: 2012
Photophysical and photochemical studies of sulfur containing phthalocyanine derivatives in the presence of folic acid
- Nombona, Nolwazi, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243180 , vital:51124 , xlink:href="https://doi.org/10.1016/j.ica.2012.03.051"
- Description: The syntheses of zinc and magnesium 9,16,23-tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyaninato complexes are described for the first time. The photophysical and photochemical parameters of these molecules in the absence or presence of folic acid are compared to the corresponding oxygen bridged complexes and to 2,9,17,23-tetrakis-[(1,6-hexanedithiol)phthalocyaninato]zinc(II), [8,15,22-tris-(naptho)-2-(amidoethanethiol)phthalocyaninato]zinc(II) and zinc phthalocyanine tetrasulfonate. In the absence of folic acid, the complexes show relatively good triplet quantum yields (ranging from 0.52 to 0.88) in DMSO with reasonable triplet lifetime between 140 and 470 μs. The complexes showed high singlet oxygen quantum yield values ranging from 0.27 to 0.66 in the absence of folic acid. In the presence of folic acid, the triplet quantum yield values were between 0.37 and 0.75 and the lifetimes were significantly reduced (70–320 μs).
- Full Text:
- Date Issued: 2012
- Authors: Nombona, Nolwazi , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243180 , vital:51124 , xlink:href="https://doi.org/10.1016/j.ica.2012.03.051"
- Description: The syntheses of zinc and magnesium 9,16,23-tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyaninato complexes are described for the first time. The photophysical and photochemical parameters of these molecules in the absence or presence of folic acid are compared to the corresponding oxygen bridged complexes and to 2,9,17,23-tetrakis-[(1,6-hexanedithiol)phthalocyaninato]zinc(II), [8,15,22-tris-(naptho)-2-(amidoethanethiol)phthalocyaninato]zinc(II) and zinc phthalocyanine tetrasulfonate. In the absence of folic acid, the complexes show relatively good triplet quantum yields (ranging from 0.52 to 0.88) in DMSO with reasonable triplet lifetime between 140 and 470 μs. The complexes showed high singlet oxygen quantum yield values ranging from 0.27 to 0.66 in the absence of folic acid. In the presence of folic acid, the triplet quantum yield values were between 0.37 and 0.75 and the lifetimes were significantly reduced (70–320 μs).
- Full Text:
- Date Issued: 2012
Photophysics and photochemistry of octaglucosylated zinc phthalocyanine derivatives
- Iqbal, Zafar, Ogunsipe, Abimbola, Nyokong, Tebello, Lyubimtsev, Alexey, Hanack, Michael, Ziegler, Thomas
- Authors: Iqbal, Zafar , Ogunsipe, Abimbola , Nyokong, Tebello , Lyubimtsev, Alexey , Hanack, Michael , Ziegler, Thomas
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244416 , vital:51255 , xlink:href="https://doi.org/10.1142/S1088424612500630"
- Description: The ground state electronic absorption spectra, photophysics and photochemistry of amphiphilic octaglucosylated zinc phthalocyanines containing oxygen or sulfur bridges are presented. Triplet quantum yield values for the two dyes (in DMF and DMSO) vary between 0.71 and 0.84, while singlet quantum yield values lie between 0.63 and 0.75. Fluorescence lifetimes were determined experimentally by time correlated single photon counting and semi-empirically by fluorescence quenching techniques; and values from both methods were within the same range. Kinetic data were obtained for the quenching of the triplet state of the phthalocyanines by ground state molecular oxygen; the bimolecular collisional quenching rate constant range between 2.35 × 108 and 1.13 × 109 M-1.s-1. These values suggest that triplet states of the dyes are effectively quenched by ground molecular oxygen.
- Full Text:
- Date Issued: 2012
- Authors: Iqbal, Zafar , Ogunsipe, Abimbola , Nyokong, Tebello , Lyubimtsev, Alexey , Hanack, Michael , Ziegler, Thomas
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244416 , vital:51255 , xlink:href="https://doi.org/10.1142/S1088424612500630"
- Description: The ground state electronic absorption spectra, photophysics and photochemistry of amphiphilic octaglucosylated zinc phthalocyanines containing oxygen or sulfur bridges are presented. Triplet quantum yield values for the two dyes (in DMF and DMSO) vary between 0.71 and 0.84, while singlet quantum yield values lie between 0.63 and 0.75. Fluorescence lifetimes were determined experimentally by time correlated single photon counting and semi-empirically by fluorescence quenching techniques; and values from both methods were within the same range. Kinetic data were obtained for the quenching of the triplet state of the phthalocyanines by ground state molecular oxygen; the bimolecular collisional quenching rate constant range between 2.35 × 108 and 1.13 × 109 M-1.s-1. These values suggest that triplet states of the dyes are effectively quenched by ground molecular oxygen.
- Full Text:
- Date Issued: 2012
Physico-chemical properties of lutetium phthalocyanine complexes in solution and in solid polystyrene polymer fibers and their application in photoconversion of 4-nitrophenol
- Zugle, Ruphino, Nyokong, Tebello
- Authors: Zugle, Ruphino , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243520 , vital:51160 , xlink:href="https://doi.org/10.1016/j.molcata.2012.02.010"
- Description: The photophysical and photochemical behavior of two phthalocyanine complexes of lutetium peripherally substituted with tetraphenoxy and tetra-2-pyridiloxy groups were studied in solution and when dispersed in polystyrene polymer fiber. The phthalocyanines were found not to fluoresce significantly in solution and not at all within the fiber matrix as compared with standard unsubstituted zinc phthalocyanine. They showed very promising photoactivity in solution with high singlet oxygen quantum yields. Their photoactivity within the polymer fiber matrix was also demonstrated with the photoconversion of 4-nitrophenol, a water pollutant. The photodegradation process with both phthalocyanines follows first order kinetics similar to that observed for the zinc phthalocyanine and the photo-products were found to be hydroquinone, benzoquinone and 4-nitrocatechol.
- Full Text:
- Date Issued: 2012
- Authors: Zugle, Ruphino , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243520 , vital:51160 , xlink:href="https://doi.org/10.1016/j.molcata.2012.02.010"
- Description: The photophysical and photochemical behavior of two phthalocyanine complexes of lutetium peripherally substituted with tetraphenoxy and tetra-2-pyridiloxy groups were studied in solution and when dispersed in polystyrene polymer fiber. The phthalocyanines were found not to fluoresce significantly in solution and not at all within the fiber matrix as compared with standard unsubstituted zinc phthalocyanine. They showed very promising photoactivity in solution with high singlet oxygen quantum yields. Their photoactivity within the polymer fiber matrix was also demonstrated with the photoconversion of 4-nitrophenol, a water pollutant. The photodegradation process with both phthalocyanines follows first order kinetics similar to that observed for the zinc phthalocyanine and the photo-products were found to be hydroquinone, benzoquinone and 4-nitrocatechol.
- Full Text:
- Date Issued: 2012
Reverse saturation absorption spectra and optical limiting properties of chlorinated tetrasubstituted phthalocyanines containing different metals
- Tuhl, Ahmad, Manaa, Hacene, Makhseed, Saad, Al-Awadi, Nouria, Matthew, Jacob, Ibrahim, Hamada Mohamed, Nyokong, Tebello, Behbehani, Haider
- Authors: Tuhl, Ahmad , Manaa, Hacene , Makhseed, Saad , Al-Awadi, Nouria , Matthew, Jacob , Ibrahim, Hamada Mohamed , Nyokong, Tebello , Behbehani, Haider
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243498 , vital:51158 , xlink:href="https://doi.org/10.1016/j.optmat.2012.05.018"
- Description: A highly non-aggregated series of peripherally tetra(2,6-diisopropylphenoxy) substituted phthalocyanines (Pcs) containing different metals (Al, Ga, In and Zn) were prepared and their nonlinear optical properties (NLO), including the optical limiting behavior were investigated. This study explores the effect of the implanted metals along with the peripheral chlorine atoms on the NLO of the prepared complexes, thereby improving their optical limiting performance. The best wavelength at which the Pc complex exhibits the strongest nonlinear effect was determined over the low absorption window region (420–590 nm) comprised between the Q and B bands using a nanosecond pulsed laser with the aid of a Z-scan technique. The excited state absorption cross sections (σeff) have been found to be wavelength dependent with common double peaks at 505 nm and around 485 nm and the highest value was calculated for Pc1–In (1.1 × 10−16 cm2). The figure of merit spectra show different spectral structure when compared to the excited state absorption spectra and the largest figure of merit value was found to be around 107 for Pc1–In derivative. In full agreement with reverse saturation results, the optical limiting measurements, carried out at 485 nm and 532 nm for each derivative, show very low optical limiting thresholds at the former wavelength. In the continuous wave excitation regime, the Z-scan measurements, which were carried out at 632.8 and 532 nm, showed strong refractive and absorptive nonlinear effects.
- Full Text:
- Date Issued: 2012
- Authors: Tuhl, Ahmad , Manaa, Hacene , Makhseed, Saad , Al-Awadi, Nouria , Matthew, Jacob , Ibrahim, Hamada Mohamed , Nyokong, Tebello , Behbehani, Haider
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243498 , vital:51158 , xlink:href="https://doi.org/10.1016/j.optmat.2012.05.018"
- Description: A highly non-aggregated series of peripherally tetra(2,6-diisopropylphenoxy) substituted phthalocyanines (Pcs) containing different metals (Al, Ga, In and Zn) were prepared and their nonlinear optical properties (NLO), including the optical limiting behavior were investigated. This study explores the effect of the implanted metals along with the peripheral chlorine atoms on the NLO of the prepared complexes, thereby improving their optical limiting performance. The best wavelength at which the Pc complex exhibits the strongest nonlinear effect was determined over the low absorption window region (420–590 nm) comprised between the Q and B bands using a nanosecond pulsed laser with the aid of a Z-scan technique. The excited state absorption cross sections (σeff) have been found to be wavelength dependent with common double peaks at 505 nm and around 485 nm and the highest value was calculated for Pc1–In (1.1 × 10−16 cm2). The figure of merit spectra show different spectral structure when compared to the excited state absorption spectra and the largest figure of merit value was found to be around 107 for Pc1–In derivative. In full agreement with reverse saturation results, the optical limiting measurements, carried out at 485 nm and 532 nm for each derivative, show very low optical limiting thresholds at the former wavelength. In the continuous wave excitation regime, the Z-scan measurements, which were carried out at 632.8 and 532 nm, showed strong refractive and absorptive nonlinear effects.
- Full Text:
- Date Issued: 2012
Schottky barrier diode parameters of Ag/MgPc/p-Si structure
- Canlıca, Mevlüde, Coskun, Mustafa, Altındal, Ahmet, Nyokong, Tebello
- Authors: Canlıca, Mevlüde , Coskun, Mustafa , Altındal, Ahmet , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245820 , vital:51408 , xlink:href="https://doi.org/10.1142/S1088424612500824"
- Description: An Ag/Pc/p-Si Schottky barrier (SB) diode was fabricated. The current-voltage (I-V), capacitance-voltage (C-V) and conductance-voltage (G-V) measurements were carried out to determine the characteristic parameters such as barrier height, ideality factor and series resistance of the SB diode. The non-linear behavior of ln (I) vs. ln (V) and ln (I/V) vs. V1/2 plots indicated that the thermoionic emission theory can be applied to evaluate junction parameters for the investigated SB diode rather than space-charge limited conduction (SCLC) mechanism and bulk-limited Poole–Frenkel emission. The bulk doping concentration NB and fixed oxide charges Nf was determined from the measured high frequency C-V curve and was found to be 9.5 × 1014 cm-3 and 2.3 × 1013 cm-2, respectively. The values of barrier height obtained from Norde's function were compared with those from the forward bias current-voltage characteristic, and it was seen that there was a good agreement between barrier heights from both methods.
- Full Text:
- Date Issued: 2012
- Authors: Canlıca, Mevlüde , Coskun, Mustafa , Altındal, Ahmet , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245820 , vital:51408 , xlink:href="https://doi.org/10.1142/S1088424612500824"
- Description: An Ag/Pc/p-Si Schottky barrier (SB) diode was fabricated. The current-voltage (I-V), capacitance-voltage (C-V) and conductance-voltage (G-V) measurements were carried out to determine the characteristic parameters such as barrier height, ideality factor and series resistance of the SB diode. The non-linear behavior of ln (I) vs. ln (V) and ln (I/V) vs. V1/2 plots indicated that the thermoionic emission theory can be applied to evaluate junction parameters for the investigated SB diode rather than space-charge limited conduction (SCLC) mechanism and bulk-limited Poole–Frenkel emission. The bulk doping concentration NB and fixed oxide charges Nf was determined from the measured high frequency C-V curve and was found to be 9.5 × 1014 cm-3 and 2.3 × 1013 cm-2, respectively. The values of barrier height obtained from Norde's function were compared with those from the forward bias current-voltage characteristic, and it was seen that there was a good agreement between barrier heights from both methods.
- Full Text:
- Date Issued: 2012
Single walled carbon nanotubes functionalized with nickel phthalocyanines
- Khene, Samson, Nyokong, Tebello
- Authors: Khene, Samson , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245843 , vital:51410 , xlink:href="https://doi.org/10.1142/S1088424611004439"
- Description: In this work we report on electrochemical behavior of nickel phthalocyanine derivatives tetrasubstituted peripherally and non-peripherally with hydroxy and used to modify single walled carbon nanotubes. Nickel phthalocyanine complex octasubstituted at the peripheral positions with hydroxy groups was also used to modify single walled carbon nanotubes. Nickel phthalocyanine complex tetrasubstituted with amino groups at peripheral position was covalently and non-covalently linked to single walled carbon nanotubes. All the conjugates of nickel phthalocyanine derivatives with single walled carbon nanotubes were used for the electro oxidation of 4-chlorophenol. The nickel phthalocyanine octabsubstituted with hydroxy groups at the non-peripheral positions gave the best current response and the best resistance against electrode fouling for the oxidation of 4-chlorophenol.
- Full Text:
- Date Issued: 2012
- Authors: Khene, Samson , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245843 , vital:51410 , xlink:href="https://doi.org/10.1142/S1088424611004439"
- Description: In this work we report on electrochemical behavior of nickel phthalocyanine derivatives tetrasubstituted peripherally and non-peripherally with hydroxy and used to modify single walled carbon nanotubes. Nickel phthalocyanine complex octasubstituted at the peripheral positions with hydroxy groups was also used to modify single walled carbon nanotubes. Nickel phthalocyanine complex tetrasubstituted with amino groups at peripheral position was covalently and non-covalently linked to single walled carbon nanotubes. All the conjugates of nickel phthalocyanine derivatives with single walled carbon nanotubes were used for the electro oxidation of 4-chlorophenol. The nickel phthalocyanine octabsubstituted with hydroxy groups at the non-peripheral positions gave the best current response and the best resistance against electrode fouling for the oxidation of 4-chlorophenol.
- Full Text:
- Date Issued: 2012
Spectral, photophysical and photochemical properties of tetra-and octaglycosylated zinc phthalocyanines
- Iqbal, Zafar, Masilela, Nkosiphile, Nyokong, Tebello, Lyubimtsev, Alexey, Hanack, Michael, Ziegler, Thomas
- Authors: Iqbal, Zafar , Masilela, Nkosiphile , Nyokong, Tebello , Lyubimtsev, Alexey , Hanack, Michael , Ziegler, Thomas
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244428 , vital:51256 , xlink:href="https://doi.org/10.1039/c2pp05348a"
- Description: Photophysical and photochemical properties of a series of tetra- and octaglycosylated zinc phthalocyanines (ZnPcs) substituted with glucose and galactose moieties have been reported. Spectral properties of these phthalocyanines are compared in DMSO. Absorption spectra of the non-peripherally tetra-substituted ZnPcs 2 showed a significant red shift in their Q-band maxima as compared to the peripherally substituted analog 1. All the complexes gave high triplet quantum yields ranging from 0.68 to 0.88, whereas triplet lifetimes were in the range of 100–430 µs in argon-saturated solutions. The octagalactosylated ZnPc 3b showed the highest triplet quantum yield and singlet oxygen quantum yield of 0.88 and 0.69, respectively. The fluorescence quantum yields and lifetimes of all the compounds under investigation were within the range of zinc phthalocyanine complexes.
- Full Text:
- Date Issued: 2012
- Authors: Iqbal, Zafar , Masilela, Nkosiphile , Nyokong, Tebello , Lyubimtsev, Alexey , Hanack, Michael , Ziegler, Thomas
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244428 , vital:51256 , xlink:href="https://doi.org/10.1039/c2pp05348a"
- Description: Photophysical and photochemical properties of a series of tetra- and octaglycosylated zinc phthalocyanines (ZnPcs) substituted with glucose and galactose moieties have been reported. Spectral properties of these phthalocyanines are compared in DMSO. Absorption spectra of the non-peripherally tetra-substituted ZnPcs 2 showed a significant red shift in their Q-band maxima as compared to the peripherally substituted analog 1. All the complexes gave high triplet quantum yields ranging from 0.68 to 0.88, whereas triplet lifetimes were in the range of 100–430 µs in argon-saturated solutions. The octagalactosylated ZnPc 3b showed the highest triplet quantum yield and singlet oxygen quantum yield of 0.88 and 0.69, respectively. The fluorescence quantum yields and lifetimes of all the compounds under investigation were within the range of zinc phthalocyanine complexes.
- Full Text:
- Date Issued: 2012
Spectroscopic and physicochemical behavior of magnesium phthalocyanine derivatives mono-substituted with a carboxylic acid group
- Nombona, Nolwazi, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244450 , vital:51258 , xlink:href="https://doi.org/10.1016/j.molstruc.2011.12.051"
- Description: This work reports on the synthesis of novel unsymmetrically substituted magnesium phthalocyanine complexes containing one carboxyl group. The physicochemical behavior of these complexes were compared with those of their unmetallated and zinc counterparts. The MgPcs showed interesting absorption spectra with [8,15,22-Tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenyl)phthalocyaninato]magnesium (II) showing a large split in the Q band whereas [8,15,22-Tris-(naphtho)-2-(carboxy) phthalocyaninato]magnesium(II) presented only a small splitting. The magnesium phthalocyanine derivatives displayed higher fluorescence quantum yields compared to unmetallated and zinc phthalocyanine counterparts. The latter gave admirable triplet and singlet oxygen quantum yields. These molecules can distinctly be employed in the field of photodynamic therapy in combination with fluorescence imaging.
- Full Text:
- Date Issued: 2012
- Authors: Nombona, Nolwazi , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244450 , vital:51258 , xlink:href="https://doi.org/10.1016/j.molstruc.2011.12.051"
- Description: This work reports on the synthesis of novel unsymmetrically substituted magnesium phthalocyanine complexes containing one carboxyl group. The physicochemical behavior of these complexes were compared with those of their unmetallated and zinc counterparts. The MgPcs showed interesting absorption spectra with [8,15,22-Tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenyl)phthalocyaninato]magnesium (II) showing a large split in the Q band whereas [8,15,22-Tris-(naphtho)-2-(carboxy) phthalocyaninato]magnesium(II) presented only a small splitting. The magnesium phthalocyanine derivatives displayed higher fluorescence quantum yields compared to unmetallated and zinc phthalocyanine counterparts. The latter gave admirable triplet and singlet oxygen quantum yields. These molecules can distinctly be employed in the field of photodynamic therapy in combination with fluorescence imaging.
- Full Text:
- Date Issued: 2012
Surface electrochemistry : structured electrode, synthesis, and characterization
- Bedioui, Fethi, Nyokong, Tebello, Zagal, Jose H
- Authors: Bedioui, Fethi , Nyokong, Tebello , Zagal, Jose H
- Date: 2012
- Language: English
- Type: Article
- Identifier: vital:6567 , http://hdl.handle.net/10962/d1004126 , http://dx.doi.org/10.1155/2012/405825
- Description: From introduction: The aim of this special issue is to show, through recent updated significant examples, how the electrochemical techniques allow the unique characterization of specific properties of micro- and nanostructured materials that offer varied possibilities of uses and the preparation of specific types of ordered materials that take advantage of electrochemical synthetic methods such as structuring nanosized wires and dots, to cite only two examples.
- Full Text:
- Date Issued: 2012
- Authors: Bedioui, Fethi , Nyokong, Tebello , Zagal, Jose H
- Date: 2012
- Language: English
- Type: Article
- Identifier: vital:6567 , http://hdl.handle.net/10962/d1004126 , http://dx.doi.org/10.1155/2012/405825
- Description: From introduction: The aim of this special issue is to show, through recent updated significant examples, how the electrochemical techniques allow the unique characterization of specific properties of micro- and nanostructured materials that offer varied possibilities of uses and the preparation of specific types of ordered materials that take advantage of electrochemical synthetic methods such as structuring nanosized wires and dots, to cite only two examples.
- 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 photophysical properties of covalent conjugates of aqua platinum (II) and octacarboxy-substituted zinc phthalocyanine
- Bulgakov, Roman A, Kuznetsova, Nina A, Dolotova, Olga V, Solovieva, Ludmila I, Mack, John, Chidawanyika, Wadzanai J U, Kaliya, Oleg L, Nyokong, Tebello
- Authors: Bulgakov, Roman A , Kuznetsova, Nina A , Dolotova, Olga V , Solovieva, Ludmila I , Mack, John , Chidawanyika, Wadzanai J U , Kaliya, Oleg L , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242726 , vital:51073 , xlink:href="https://doi.org/10.1142/S1088424612501209"
- Description: New covalent conjugates of aqua platinum(II) and octacarboxy-substituted zinc phthalocyanine, bearing one, two, three and four aqua platinum moieties on the periphery of the Pc ligand have been synthesized and characterized. The effect of the stepwise introduction of the aqua platinums on the photophysical and photochemical properties of these compounds has been investigated in dimethylsulfoxide solution. It has been found that aqua platinum moieties have only a limited effect on the dynamics of the singlet and triplet excited states, on the ability to sensitize singlet oxygen formation and on the photostability. Each conjugate has a high singlet oxygen quantum yield (ΦΔ 0.51–0.62) and thus retains potential for use as a dual action anticancer drugs by acting as a sensitizer for PDT in addition to the likely chemotherapeutic effects of the Pt(II) complexes.
- Full Text:
- Date Issued: 2012
- Authors: Bulgakov, Roman A , Kuznetsova, Nina A , Dolotova, Olga V , Solovieva, Ludmila I , Mack, John , Chidawanyika, Wadzanai J U , Kaliya, Oleg L , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242726 , vital:51073 , xlink:href="https://doi.org/10.1142/S1088424612501209"
- Description: New covalent conjugates of aqua platinum(II) and octacarboxy-substituted zinc phthalocyanine, bearing one, two, three and four aqua platinum moieties on the periphery of the Pc ligand have been synthesized and characterized. The effect of the stepwise introduction of the aqua platinums on the photophysical and photochemical properties of these compounds has been investigated in dimethylsulfoxide solution. It has been found that aqua platinum moieties have only a limited effect on the dynamics of the singlet and triplet excited states, on the ability to sensitize singlet oxygen formation and on the photostability. Each conjugate has a high singlet oxygen quantum yield (ΦΔ 0.51–0.62) and thus retains potential for use as a dual action anticancer drugs by acting as a sensitizer for PDT in addition to the likely chemotherapeutic effects of the Pt(II) complexes.
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- Date Issued: 2012