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
Oxovanadium (IV)-containing poly (styrene-co-4′-ethenyl-2-hydroxyphenylimidazole) electrospun nanofibers for the catalytic oxidation of thioanisole
- Walmsley, Ryan S, Litwinski, Christian, Antunes, Edith M, Hlangothi, Percy, Hosten, Eric, McCleland, Cedric, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Walmsley, Ryan S , Litwinski, Christian , Antunes, Edith M , Hlangothi, Percy , Hosten, Eric , McCleland, Cedric , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241665 , vital:50959 , xlink:href="https://doi.org/10.1016/j.molcata.2013.07.018"
- Description: The catalytic fibers have been fabricated by the electrospinning of a copolymer of styrene and 2-(2′-hydroxy-4′-ethenylphenyl)imidazole {p(ST-co-VPIM)} followed by a reaction with a methanolic vanadyl solution to afford the oxovanadium(IV)-containing poly(styrene-co-4′-ethenyl-2-hydroxyphenylimidazole) fibers {p(ST-co-VPIM)-VO fibers}. The relationship between polymer concentration and fiber diameter was investigated, and at high concentration (20 wt%) the fibers were quite large (average diameter of 3.8 μm) but as the concentration was reduced fibers of much lower diameter were produced (0.6 μm using 8 wt%). The BET surface area for p(ST-co-VPIM) fibers (0.6 μm diameter) was 47.9 m2 g−1 and functionalization of p(ST-co-VPIM) with vanadyl resulted in an increase in surface area to 60.7 m2 g−1 for p(ST-co-VPIM)-VO. The presence of vanadyl was confirmed by XPS and EPR. The EPR spectral analyses depicted complex speciation of vanadium within these polymer supports. These catalytic fibers were applied under batch and continuous flow conditions for the catalytic oxidation of thioanisole using hydrogen peroxide. The continuous flow method gave excellent and constant conversion throughout the 10 h period studied. The leaching of vanadium from the fiber support was 4% over the 10 h period indicating a significant stability of the material.
- Full Text:
- Date Issued: 2013
- Authors: Walmsley, Ryan S , Litwinski, Christian , Antunes, Edith M , Hlangothi, Percy , Hosten, Eric , McCleland, Cedric , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241665 , vital:50959 , xlink:href="https://doi.org/10.1016/j.molcata.2013.07.018"
- Description: The catalytic fibers have been fabricated by the electrospinning of a copolymer of styrene and 2-(2′-hydroxy-4′-ethenylphenyl)imidazole {p(ST-co-VPIM)} followed by a reaction with a methanolic vanadyl solution to afford the oxovanadium(IV)-containing poly(styrene-co-4′-ethenyl-2-hydroxyphenylimidazole) fibers {p(ST-co-VPIM)-VO fibers}. The relationship between polymer concentration and fiber diameter was investigated, and at high concentration (20 wt%) the fibers were quite large (average diameter of 3.8 μm) but as the concentration was reduced fibers of much lower diameter were produced (0.6 μm using 8 wt%). The BET surface area for p(ST-co-VPIM) fibers (0.6 μm diameter) was 47.9 m2 g−1 and functionalization of p(ST-co-VPIM) with vanadyl resulted in an increase in surface area to 60.7 m2 g−1 for p(ST-co-VPIM)-VO. The presence of vanadyl was confirmed by XPS and EPR. The EPR spectral analyses depicted complex speciation of vanadium within these polymer supports. These catalytic fibers were applied under batch and continuous flow conditions for the catalytic oxidation of thioanisole using hydrogen peroxide. The continuous flow method gave excellent and constant conversion throughout the 10 h period studied. The leaching of vanadium from the fiber support was 4% over the 10 h period indicating a significant stability of the material.
- Full Text:
- Date Issued: 2013
Electrospun fibers functionalized with phthalocyanine-gold nanoparticle conjugates for photocatalytic applications
- Tombe, Sekai, Antunes, Edith M, Nyokong, Tebello
- Authors: Tombe, Sekai , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193769 , vital:45394 , xlink:href="https://doi.org/10.1016/j.molcata.2013.01.033"
- Description: The heterogeneous photocatalytic activity of Zn(II) phthalocyanine-gold nanoparticle conjugates immobilized on electrospun polystyrene fibers was investigated using 4-chlorophenol and Orange G as model pollutants. The phthalocyanine-gold nanoparticle conjugates were synthesized via a ligand exchange reaction and characterized using spectroscopic and microscopic techniques. The interaction between the gold nanoparticles and phthalocyanines did not restrict the formation of excited singlet states, triplet states and hence the formation of singlet oxygen required for photocatalysis. The conjugates showed significantly higher singlet oxygen quantum yields and enhanced photocatalytic activity compared to the phthalocyanines. It was concluded that hybrid electrospun fibers provide great potential as active photocatalysts for oxidizing organic pollutants using singlet oxygen as an oxidant.
- Full Text:
- Date Issued: 2013
- Authors: Tombe, Sekai , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193769 , vital:45394 , xlink:href="https://doi.org/10.1016/j.molcata.2013.01.033"
- Description: The heterogeneous photocatalytic activity of Zn(II) phthalocyanine-gold nanoparticle conjugates immobilized on electrospun polystyrene fibers was investigated using 4-chlorophenol and Orange G as model pollutants. The phthalocyanine-gold nanoparticle conjugates were synthesized via a ligand exchange reaction and characterized using spectroscopic and microscopic techniques. The interaction between the gold nanoparticles and phthalocyanines did not restrict the formation of excited singlet states, triplet states and hence the formation of singlet oxygen required for photocatalysis. The conjugates showed significantly higher singlet oxygen quantum yields and enhanced photocatalytic activity compared to the phthalocyanines. It was concluded that hybrid electrospun fibers provide great potential as active photocatalysts for oxidizing organic pollutants using singlet oxygen as an oxidant.
- Full Text:
- Date Issued: 2013
The photophysical and photochemical behaviour of coumarin-derivatized zinc phthalocyanine when conjugated with gold nanoparticles and electrospun into polymer fibers
- Tombe, Sekai, Antunes, Edith M, Nyokong, Tebello
- Authors: Tombe, Sekai , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232534 , vital:50000 , xlink:href="https://doi.org/10.1039/C2NJ40984D"
- Description: Polymer composite fibers doped with phthalocyanines and phthalocyanine-functionalized gold nanoparticles were developed. The phthalocyanine and phthalocyanine-functionalized gold nanoparticles have been characterized using UV/Vis, fluorescence and X-ray photoelectron spectroscopy (XPS), time correlated single photon counting (TCSPC), time-resolved emission spectra (TRES) and transmission electron microscopy (TEM). The changes in photophysical and photochemical behavior of the phthalocyanines induced by their interaction with gold nanoparticles and polystyrene were also investigated. In the presence of gold nanoparticles, the fluorescence lifetimes and quantum yields of the phthalocyanine decreased, whereas the singlet oxygen quantum yield increased. This work shows that polymer composite fibers could be used as functional fibers for a variety of applications such as gas sensing when using the advantageous properties of phthalocyanines and gold nanoparticles.
- Full Text:
- Date Issued: 2013
- Authors: Tombe, Sekai , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232534 , vital:50000 , xlink:href="https://doi.org/10.1039/C2NJ40984D"
- Description: Polymer composite fibers doped with phthalocyanines and phthalocyanine-functionalized gold nanoparticles were developed. The phthalocyanine and phthalocyanine-functionalized gold nanoparticles have been characterized using UV/Vis, fluorescence and X-ray photoelectron spectroscopy (XPS), time correlated single photon counting (TCSPC), time-resolved emission spectra (TRES) and transmission electron microscopy (TEM). The changes in photophysical and photochemical behavior of the phthalocyanines induced by their interaction with gold nanoparticles and polystyrene were also investigated. In the presence of gold nanoparticles, the fluorescence lifetimes and quantum yields of the phthalocyanine decreased, whereas the singlet oxygen quantum yield increased. This work shows that polymer composite fibers could be used as functional fibers for a variety of applications such as gas sensing when using the advantageous properties of phthalocyanines and gold nanoparticles.
- Full Text:
- Date Issued: 2013
Synthesis and characterization of Na (Y, Gd) F4 upconversion nanoparticles and an investigation of their effects on the photophysical properties of an unsubstituted tetrathiophenoxy phthalocyanine
- Taylor, Jessica M, Litwinski, Christian, Nyokong, Tebello, Antunes, Edith M
- Authors: Taylor, Jessica M , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241437 , vital:50939 , xlink:href="https://doi.org/10.1007/s11051-015-2889-5"
- Description: Sphere- and star-shaped Na(Y,Gd)F4:Yb/Er(Tm)upconversion nanoparticles (UCNP) were successfully synthesized utilizing a methanol-assisted thermal decomposition approach and their spectroscopic (absorption, emission and luminescence lifetime) properties fully characterized. The factors affecting the size and shape of the UCNPs were studied and discussed in detail. The size of the nanoparticles was determined using TEM primarily and found to be approximately 19 and 30 nm for the Er and Tm spheres, respectively, while the Er and Tm “stars” were found to be much larger with sizes ranging from 110 to 240 nm, respectively (as determined along the width of the nanoparticle). In addition, their influence on the spectroscopic properties of an unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) was investigated. The UCNP were found to produce characteristic upconversion luminescence emissions in the blue, green, red and NIR regions. Simple mixing with an H2Pc in toluene was found to exert no obvious changes in the spectroscopic properties of the Pc, although a considerable increase in the radiative lifetimes is observed for the Pc in the presence of the UCNPs. The singlet oxygen generation mediated by the red light excitation of the H2Pc mixed with UCNP was found to decrease in the presence of the NPs.
- Full Text:
- Date Issued: 2015
- Authors: Taylor, Jessica M , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241437 , vital:50939 , xlink:href="https://doi.org/10.1007/s11051-015-2889-5"
- Description: Sphere- and star-shaped Na(Y,Gd)F4:Yb/Er(Tm)upconversion nanoparticles (UCNP) were successfully synthesized utilizing a methanol-assisted thermal decomposition approach and their spectroscopic (absorption, emission and luminescence lifetime) properties fully characterized. The factors affecting the size and shape of the UCNPs were studied and discussed in detail. The size of the nanoparticles was determined using TEM primarily and found to be approximately 19 and 30 nm for the Er and Tm spheres, respectively, while the Er and Tm “stars” were found to be much larger with sizes ranging from 110 to 240 nm, respectively (as determined along the width of the nanoparticle). In addition, their influence on the spectroscopic properties of an unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) was investigated. The UCNP were found to produce characteristic upconversion luminescence emissions in the blue, green, red and NIR regions. Simple mixing with an H2Pc in toluene was found to exert no obvious changes in the spectroscopic properties of the Pc, although a considerable increase in the radiative lifetimes is observed for the Pc in the presence of the UCNPs. The singlet oxygen generation mediated by the red light excitation of the H2Pc mixed with UCNP was found to decrease in the presence of the NPs.
- Full Text:
- Date Issued: 2015
Synthesis and characterization of Na(Y,Gd)F4 upconversion nanoparticles and an investigation of their effects on the photophysical properties of an unsubstituted tetrathiophenoxy phthalocyanine
- Taylor, Jessica M, Litwinski, Christian, Nyokong, Tebello, Antunes, Edith M
- Authors: Taylor, Jessica M , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Language: English
- Type: Article
- Identifier: vital:7253 , http://hdl.handle.net/10962/d1020261
- Description: Sphere- and star-shaped Na(Y,Gd)F4:Yb/Er(Tm)upconversion nanoparticles (UCNP) were successfully synthesized utilizing a methanol-assisted thermal decomposition approach and their spectroscopic (absorption, emission and luminescence lifetime) properties fully characterized. The factors affecting the size and shape of the UCNPs were studied and discussed in detail. The size of the nanoparticles was determined using TEM primarily and found to be approximately 19 and 30 nm for the Er and Tm spheres, respectively, while the Er and Tm “stars” were found to be much larger with sizes ranging from 110 to 240 nm, respectively (as determined along the width of the nanoparticle). In addition, their influence on the spectroscopic properties of an unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) was investigated. The UCNP were found to produce characteristic upconversion luminescence emissions in the blue, green, red and NIR regions. Simple mixing with an H2Pc in toluene was found to exert no obvious changes in the spectroscopic properties of the Pc, although a considerable increase in the radiative lifetimes is observed for the Pc in the presence of the UCNPs. The singlet oxygen generation mediated by the red light excitation of the H2Pc mixed with UCNP was found to decrease in the presence of the NPs. , Original publication is available at http://dx.doi.org/10.1007/s11051-015-2889-5
- Full Text: false
- Authors: Taylor, Jessica M , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Language: English
- Type: Article
- Identifier: vital:7253 , http://hdl.handle.net/10962/d1020261
- Description: Sphere- and star-shaped Na(Y,Gd)F4:Yb/Er(Tm)upconversion nanoparticles (UCNP) were successfully synthesized utilizing a methanol-assisted thermal decomposition approach and their spectroscopic (absorption, emission and luminescence lifetime) properties fully characterized. The factors affecting the size and shape of the UCNPs were studied and discussed in detail. The size of the nanoparticles was determined using TEM primarily and found to be approximately 19 and 30 nm for the Er and Tm spheres, respectively, while the Er and Tm “stars” were found to be much larger with sizes ranging from 110 to 240 nm, respectively (as determined along the width of the nanoparticle). In addition, their influence on the spectroscopic properties of an unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) was investigated. The UCNP were found to produce characteristic upconversion luminescence emissions in the blue, green, red and NIR regions. Simple mixing with an H2Pc in toluene was found to exert no obvious changes in the spectroscopic properties of the Pc, although a considerable increase in the radiative lifetimes is observed for the Pc in the presence of the UCNPs. The singlet oxygen generation mediated by the red light excitation of the H2Pc mixed with UCNP was found to decrease in the presence of the NPs. , Original publication is available at http://dx.doi.org/10.1007/s11051-015-2889-5
- Full Text: false
Fluorescence Behaviour of an Aluminium Octacarboxy Phthalocyanine-NaYGdF 4
- Taylor, Jessica, Litwinski, Christian, Nyokong, Tebello, Antunes, Edith M
- Authors: Taylor, Jessica , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189503 , vital:44852 , xlink:href="https://doi.org/10.1007/s10895-015-1539-8"
- Description: Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine’s Q band, which was accompanied by a decrease in the Pc’s fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle’s and phthalocyanine’s emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd3+ ions).
- Full Text:
- Date Issued: 2015
- Authors: Taylor, Jessica , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189503 , vital:44852 , xlink:href="https://doi.org/10.1007/s10895-015-1539-8"
- Description: Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine’s Q band, which was accompanied by a decrease in the Pc’s fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle’s and phthalocyanine’s emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd3+ ions).
- Full Text:
- Date Issued: 2015
Fluorescence Behaviour of an Aluminium Octacarboxy Phthalocyanine - NaYGdF4:Yb/Er Nanoparticle Conjugate
- Taylor, Jessica, Litwinski, Christian, Nyokong, Tebello, Antunes, Edith M
- Authors: Taylor, Jessica , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Language: English
- Type: Article
- Identifier: vital:7247 , http://hdl.handle.net/10962/d1020252
- Description: Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine’s Q band, which was accompanied by a decrease in the Pc’s fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle’s and phthalocyanine’s emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd3+ ions). , Original publication is available at http://dx.doi.org/10.1007/s10895-015-1539-8
- Full Text: false
- Authors: Taylor, Jessica , Litwinski, Christian , Nyokong, Tebello , Antunes, Edith M
- Language: English
- Type: Article
- Identifier: vital:7247 , http://hdl.handle.net/10962/d1020252
- Description: Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine’s Q band, which was accompanied by a decrease in the Pc’s fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle’s and phthalocyanine’s emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd3+ ions). , Original publication is available at http://dx.doi.org/10.1007/s10895-015-1539-8
- Full Text: false
Fluorescence behavior of glutathione capped CdTe@ ZnS quantum dots chemically coordinated to zinc octacarboxy phthalocyanines
- Sekhosana, Kutloano E, Antunes, Edith M, Khene, Samson M, D'Souza, Sarah, Nyokong, Tebello
- Authors: Sekhosana, Kutloano E , Antunes, Edith M , Khene, Samson M , D'Souza, Sarah , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242019 , vital:50993 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.11.044"
- Description: Core–shell CdTe@ZnS quantum dots capped with glutathione (CdTe@ZnS–GSH) were covalently linked to zinc octacarboxy phthalocyanine (ZnPc(COOH)8). The conjugate was characterized by UV/Vis, infrared and X-Ray photoelectron spectroscopies as well as transmission electron and atomic force microscopies. The fluorescence quantum yields of the core CdTe capped with thioglycolic acid increased upon formation of the core-shell. Upon conjugation with ZnPc(COOH)8, the fluorescence quantum yield of CdTe@ZnS–GSH decreased due to energy transfer from the latter to the Pc. The average fluorescence lifetime of the CdTe@ZnS–GSH QD also decreased upon conjugation from 26.2 to 13.3 ns.
- Full Text:
- Date Issued: 2013
- Authors: Sekhosana, Kutloano E , Antunes, Edith M , Khene, Samson M , D'Souza, Sarah , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242019 , vital:50993 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.11.044"
- Description: Core–shell CdTe@ZnS quantum dots capped with glutathione (CdTe@ZnS–GSH) were covalently linked to zinc octacarboxy phthalocyanine (ZnPc(COOH)8). The conjugate was characterized by UV/Vis, infrared and X-Ray photoelectron spectroscopies as well as transmission electron and atomic force microscopies. The fluorescence quantum yields of the core CdTe capped with thioglycolic acid increased upon formation of the core-shell. Upon conjugation with ZnPc(COOH)8, the fluorescence quantum yield of CdTe@ZnS–GSH decreased due to energy transfer from the latter to the Pc. The average fluorescence lifetime of the CdTe@ZnS–GSH QD also decreased upon conjugation from 26.2 to 13.3 ns.
- Full Text:
- Date Issued: 2013
Glutathione capped CdTe@ ZnS quantum dots–zinc tetracarboxy phthalocyanine conjugates
- Sekhosana, Kutloana E, Antunes, Edith M, Nyokong, Tebello
- Authors: Sekhosana, Kutloana E , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193780 , vital:45395 , xlink:href="https://doi.org/10.1016/j.poly.2013.02.060"
- Description: Conjugates of zinc tetracarboxy phthalocyanine (ZnPc(COOH)4) with CdTe@ZnS–GSH quantum dots (QDs) were synthesized and characterized by several techniques including X-ray powder diffraction and infrared spectroscopy. There was an observed decrease in both the fluorescence quantum yields and lifetimes of the quantum dots when they were linked or mixed with ZnPc(COOH)4 due to Förster resonance energy transfer (FRET). The FRET behavior of CdTe@ZnS–GSH–ZnPc(COOH)4 conjugates was compared to that of CdTe@ZnS–GSH–ZnPc(COOH)8. Higher FRET efficiencies were observed for CdTe@ZnS–GSH–ZnPc(COOH)4-mixed or CdTe@ZnS–GSH–ZnPc(COOH)4-linked compared to the corresponding CdTe@ZnS–GSH–ZnPc(COOH)8-mixed or CdTe@ZnS–GSH–ZnPc(COOH)8-linked. Also CdTe@ZnS–GSH–ZnPc(COOH)4-mixed (containing coreshell QDs) showed higher FRET efficiency than CdTE–TGA–ZnPc(COOH)4-mixed containing core QDs. The FRET efficiencies were found to be 63% and 59% for the CdTe@ZnS–GSH–ZnPc(COOH)4-linked and CdTe@ZnS–GSH–ZnPc(COOH)4-mixed samples, respectively.
- Full Text:
- Date Issued: 2013
- Authors: Sekhosana, Kutloana E , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193780 , vital:45395 , xlink:href="https://doi.org/10.1016/j.poly.2013.02.060"
- Description: Conjugates of zinc tetracarboxy phthalocyanine (ZnPc(COOH)4) with CdTe@ZnS–GSH quantum dots (QDs) were synthesized and characterized by several techniques including X-ray powder diffraction and infrared spectroscopy. There was an observed decrease in both the fluorescence quantum yields and lifetimes of the quantum dots when they were linked or mixed with ZnPc(COOH)4 due to Förster resonance energy transfer (FRET). The FRET behavior of CdTe@ZnS–GSH–ZnPc(COOH)4 conjugates was compared to that of CdTe@ZnS–GSH–ZnPc(COOH)8. Higher FRET efficiencies were observed for CdTe@ZnS–GSH–ZnPc(COOH)4-mixed or CdTe@ZnS–GSH–ZnPc(COOH)4-linked compared to the corresponding CdTe@ZnS–GSH–ZnPc(COOH)8-mixed or CdTe@ZnS–GSH–ZnPc(COOH)8-linked. Also CdTe@ZnS–GSH–ZnPc(COOH)4-mixed (containing coreshell QDs) showed higher FRET efficiency than CdTE–TGA–ZnPc(COOH)4-mixed containing core QDs. The FRET efficiencies were found to be 63% and 59% for the CdTe@ZnS–GSH–ZnPc(COOH)4-linked and CdTe@ZnS–GSH–ZnPc(COOH)4-mixed samples, respectively.
- Full Text:
- Date Issued: 2013
Water-soluble phthalocyanines mediated photodynamic effect on mesothelioma cells
- Saydan, Nil, Durmus, Mahmut, Dizge, Meltem G, Yaman, Hanif, Gürek, Ayşe G, Antunes, Edith M, Nyokong, Tebello, Ahsen, Vefa
- Authors: Saydan, Nil , Durmus, Mahmut , Dizge, Meltem G , Yaman, Hanif , Gürek, Ayşe G , Antunes, Edith M , Nyokong, Tebello , Ahsen, Vefa
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263480 , vital:53631 , xlink:href="https://doi.org/10.1142/S1088424609000863"
- Description: The new peripherally 2-mercaptopyridine tetrasubstituted zinc phthalocyanine (2) and its quaternized derivative (3) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternized compound (3) shows excellent solubility in water, which makes it a potential photosensitizer for use in photodynamic therapy (PDT) of cancer. Fluorescence and singlet oxygen quantum yield measurements were conducted on 2-mercaptopyridine appended zinc phthalocyanines in dimethylsulphoxide (DMSO) for both the non-ionic (2) and quaternized (3) derivatives, and in aqueous media for the water-soluble complex 3. General trends are described for fluorescence and singlet oxygen quantum yields of these compounds. In this study, the cells were incubated with a novel water-soluble zinc phthalocyanine derivative (3) and thereafter the cells were illuminated using broad-band incoherent light source of various energy levels. Cytotoxicity of PDT on two pleural malign mesothelioma cell lines was determined by colorimetric proliferation assay. In addition, after PDT treatment, determination of activity matrix metalloproteinases (MMPs) were evaluated using gelatine zymography.
- Full Text:
- Date Issued: 2009
- Authors: Saydan, Nil , Durmus, Mahmut , Dizge, Meltem G , Yaman, Hanif , Gürek, Ayşe G , Antunes, Edith M , Nyokong, Tebello , Ahsen, Vefa
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263480 , vital:53631 , xlink:href="https://doi.org/10.1142/S1088424609000863"
- Description: The new peripherally 2-mercaptopyridine tetrasubstituted zinc phthalocyanine (2) and its quaternized derivative (3) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternized compound (3) shows excellent solubility in water, which makes it a potential photosensitizer for use in photodynamic therapy (PDT) of cancer. Fluorescence and singlet oxygen quantum yield measurements were conducted on 2-mercaptopyridine appended zinc phthalocyanines in dimethylsulphoxide (DMSO) for both the non-ionic (2) and quaternized (3) derivatives, and in aqueous media for the water-soluble complex 3. General trends are described for fluorescence and singlet oxygen quantum yields of these compounds. In this study, the cells were incubated with a novel water-soluble zinc phthalocyanine derivative (3) and thereafter the cells were illuminated using broad-band incoherent light source of various energy levels. Cytotoxicity of PDT on two pleural malign mesothelioma cell lines was determined by colorimetric proliferation assay. In addition, after PDT treatment, determination of activity matrix metalloproteinases (MMPs) were evaluated using gelatine zymography.
- Full Text:
- Date Issued: 2009
Nonlinear optical behavior of metal octaphenoxy phthalocyanines
- Sanusi, Sikiru O, Antunes, Edith M, Nyokong, Tebello
- Authors: Sanusi, Sikiru O , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241717 , vital:50963 , xlink:href="https://doi.org/10.1142/S1088424613500715"
- Description: In this work, we investigated the nonlinear optical absorption properties of chloroaluminum, chlorogallium, chloroindium, zinc and lead octaphenoxy phthalocyanines in a dimethyl sulphoxide solution using 5 ns pulses at 532 nm. Using the Z-scan technique, the nonlinear optical properties and the excited state absorption cross-sections were determined by fitting the Z-scan data. The k value was the highest for Pb derivative at 211, making it the best nonlinear optical material. In terms of hyperpolarizability, Pb derivative (containing a larger central metal) also gave the largest value followed by aluminum derivative (containing a small central metal). The distortion of the ring caused by the central metal is used to explain the hyperpolarizability values. Large nonlinear absorption coefficient values, βeff, in the range of 3.558–4.763 × 10-9 cm.W-1 and low saturation fluence values, Fsat between 21.5–38.5 mJ.cm-2, were obtained for these samples.
- Full Text:
- Date Issued: 2013
- Authors: Sanusi, Sikiru O , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241717 , vital:50963 , xlink:href="https://doi.org/10.1142/S1088424613500715"
- Description: In this work, we investigated the nonlinear optical absorption properties of chloroaluminum, chlorogallium, chloroindium, zinc and lead octaphenoxy phthalocyanines in a dimethyl sulphoxide solution using 5 ns pulses at 532 nm. Using the Z-scan technique, the nonlinear optical properties and the excited state absorption cross-sections were determined by fitting the Z-scan data. The k value was the highest for Pb derivative at 211, making it the best nonlinear optical material. In terms of hyperpolarizability, Pb derivative (containing a larger central metal) also gave the largest value followed by aluminum derivative (containing a small central metal). The distortion of the ring caused by the central metal is used to explain the hyperpolarizability values. Large nonlinear absorption coefficient values, βeff, in the range of 3.558–4.763 × 10-9 cm.W-1 and low saturation fluence values, Fsat between 21.5–38.5 mJ.cm-2, were obtained for these samples.
- Full Text:
- Date Issued: 2013
Optical nonlinearities in non-peripherally substituted pyridyloxy phthalocyanines
- Sanusi, Kayode, Antunes, Edith M, Nyokong, Tebello
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241618 , vital:50955 , xlink:href="https://doi.org/10.1039/C3DT52462K"
- Description: The optical nonlinearities of six non-peripherally-substituted pyridyloxy phthalocyanines have been studied at 532 nm using a nanosecond Z-scan technique in a dimethyl sulphoxide solution. Ring-strain effects and the absence of a metal center were found to greatly reduce the inherent high nonlinearities expected of some of these phthalocyanine complexes. Of the six molecules investigated, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyaninato lead(II) 3, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyanine 5, and 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyanine 6 were found to exhibit negligible nonlinear optical behavior, due to either the absence of asymmetry or central metal and/or the presence of a ring-strain effect. A two-photon absorption process was found to be the major contributor to the observed reverse saturable absorption (RSA) in 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyaninato lead(II) 4, 1(4)-mono-(2-pyridyloxy)phthalocyaninato lead(II) 7, and 1(4)-mono-(4-pyridyloxy)phthalocyaninato lead(II) 8, with large two-photon absorption cross-section, high hyperpolarizability and high third-order susceptibility values in the range of 4.53 × 10−43–5.33 × 10−42 cm4 s per photon, 1.61 × 10−28–1.89 × 10−27 esu and 9.73 × 10−12–7.05 × 10−11 esu respectively.
- Full Text:
- Date Issued: 2014
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241618 , vital:50955 , xlink:href="https://doi.org/10.1039/C3DT52462K"
- Description: The optical nonlinearities of six non-peripherally-substituted pyridyloxy phthalocyanines have been studied at 532 nm using a nanosecond Z-scan technique in a dimethyl sulphoxide solution. Ring-strain effects and the absence of a metal center were found to greatly reduce the inherent high nonlinearities expected of some of these phthalocyanine complexes. Of the six molecules investigated, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyaninato lead(II) 3, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyanine 5, and 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyanine 6 were found to exhibit negligible nonlinear optical behavior, due to either the absence of asymmetry or central metal and/or the presence of a ring-strain effect. A two-photon absorption process was found to be the major contributor to the observed reverse saturable absorption (RSA) in 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyaninato lead(II) 4, 1(4)-mono-(2-pyridyloxy)phthalocyaninato lead(II) 7, and 1(4)-mono-(4-pyridyloxy)phthalocyaninato lead(II) 8, with large two-photon absorption cross-section, high hyperpolarizability and high third-order susceptibility values in the range of 4.53 × 10−43–5.33 × 10−42 cm4 s per photon, 1.61 × 10−28–1.89 × 10−27 esu and 9.73 × 10−12–7.05 × 10−11 esu respectively.
- Full Text:
- Date Issued: 2014
Optical nonlinearities in non-peripherally substituted pyridyloxy phthalocyanines: a combined effect of symmetry, ring-strain and demetallation
- Sanusi, Kayode, Antunes, Edith M, Nyokong, Tebello
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7301 , http://hdl.handle.net/10962/d1020375
- Description: The optical nonlinearities of six non-peripherally-substituted pyridyloxy phthalocyanines have been studied at 532 nm using a nanosecond Z-scan technique in a dimethyl sulphoxide solution. Ring-strain effects and the absence of a metal center were found to greatly reduce the inherent high nonlinearities expected of some of these phthalocyanine complexes. Of the six molecules investigated, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyaninato lead(II) 3, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyanine 5, and 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyanine 6 were found to exhibit negligible nonlinear optical behavior, due to either the absence of asymmetry or central metal and/or the presence of a ring-strain effect. A two-photon absorption process was found to be the major contributor to the observed reverse saturable absorption (RSA) in 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyaninato lead(II) 4, 1(4)-mono-(2-pyridyloxy)phthalocyaninato lead(II) 7, and 1(4)-mono-(4-pyridyloxy)phthalocyaninato lead(II) 8, with large two-photon absorption cross-section, high hyperpolarizability and high third-order susceptibility values in the range of 4.53 × 10−43–5.33 × 10−42 cm4 s per photon, 1.61 × 10−28–1.89 × 10−27 esu and 9.73 × 10−12–7.05 × 10−11 esu respectively. , Original publication is available at http://dx.doi.org/10.1039/C3DT52462K , Arbortext Advanced Print Publisher 9.1.520/W Unicode , Acrobat Distiller 10.0.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
- Full Text:
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7301 , http://hdl.handle.net/10962/d1020375
- Description: The optical nonlinearities of six non-peripherally-substituted pyridyloxy phthalocyanines have been studied at 532 nm using a nanosecond Z-scan technique in a dimethyl sulphoxide solution. Ring-strain effects and the absence of a metal center were found to greatly reduce the inherent high nonlinearities expected of some of these phthalocyanine complexes. Of the six molecules investigated, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyaninato lead(II) 3, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyanine 5, and 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyanine 6 were found to exhibit negligible nonlinear optical behavior, due to either the absence of asymmetry or central metal and/or the presence of a ring-strain effect. A two-photon absorption process was found to be the major contributor to the observed reverse saturable absorption (RSA) in 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyaninato lead(II) 4, 1(4)-mono-(2-pyridyloxy)phthalocyaninato lead(II) 7, and 1(4)-mono-(4-pyridyloxy)phthalocyaninato lead(II) 8, with large two-photon absorption cross-section, high hyperpolarizability and high third-order susceptibility values in the range of 4.53 × 10−43–5.33 × 10−42 cm4 s per photon, 1.61 × 10−28–1.89 × 10−27 esu and 9.73 × 10−12–7.05 × 10−11 esu respectively. , Original publication is available at http://dx.doi.org/10.1039/C3DT52462K , Arbortext Advanced Print Publisher 9.1.520/W Unicode , Acrobat Distiller 10.0.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
- Full Text:
A study of the photophysicochemical and antimicrobial properties of two zinc phthalocyanine–silver nanoparticle conjugates
- Rapulenyane, Nomasonto, Antunes, Edith M, Nyokong, Tebello
- Authors: Rapulenyane, Nomasonto , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232522 , vital:49999 , xlink:href="https://doi.org/10.1039/C3NJ41107A"
- Description: This work reports conjugation of two mono carboxy substituted zinc phthalocyanines with glutathione capped silver nanoparticles (GSH-AgNPs). The photophysicochemical behaviour of the novel phthalocyanines–silver nanoparticle conjugates was investigated together with simple mixtures of the silver nanoparticles with low symmetry phthalocyanines (i.e. with no direct chemical bond formation). It was observed that upon conjugation of the phthalocyanines to the silver nanoparticles, a blue shifting of the Q band was induced. The triplet lifetimes and quantum yields improved upon conjugation as compared to the phthalocyanines alone. Fluorescence lifetimes and quantum yields decreased for conjugates compared to the phthalocyanines alone due to quenching caused by the silver nanoparticles. The low symmetry phthalocyanines and their conjugates showed antimicrobial activity against Escherichia coli in the presence and absence of light.
- Full Text:
- Date Issued: 2013
- Authors: Rapulenyane, Nomasonto , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232522 , vital:49999 , xlink:href="https://doi.org/10.1039/C3NJ41107A"
- Description: This work reports conjugation of two mono carboxy substituted zinc phthalocyanines with glutathione capped silver nanoparticles (GSH-AgNPs). The photophysicochemical behaviour of the novel phthalocyanines–silver nanoparticle conjugates was investigated together with simple mixtures of the silver nanoparticles with low symmetry phthalocyanines (i.e. with no direct chemical bond formation). It was observed that upon conjugation of the phthalocyanines to the silver nanoparticles, a blue shifting of the Q band was induced. The triplet lifetimes and quantum yields improved upon conjugation as compared to the phthalocyanines alone. Fluorescence lifetimes and quantum yields decreased for conjugates compared to the phthalocyanines alone due to quenching caused by the silver nanoparticles. The low symmetry phthalocyanines and their conjugates showed antimicrobial activity against Escherichia coli in the presence and absence of light.
- Full Text:
- Date Issued: 2013
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
Cyclic voltammetry and spectroelectrochemistry of a novel manganese phthalocyanine substituted with hexynyl groups
- Quinton, Damien, Antunes, Edith M, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Quinton, Damien , Antunes, Edith M , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248450 , vital:51687 , xlink:href="https://doi.org/10.1016/j.inoche.2010.11.029"
- Description: We report here on the synthesis of a new manganese phthalocyanine complex, namely Mn tetrakis(5-hexyn-oxy) phthalocyanine (3), specifically designed to possess an alkyne moiety for its potential use in controlled immobilization on electrodes via the so called “click” chemistry reaction. The electrochemical activity of complex 3 was investigated by cyclic voltammetry and the nature of the observed redox couples was elucidated by spectroelectrochemistry. This work has also shown that the reduction of Mn(III)Pc complex to Mn(II)Pc is accompanied by the formation of MnPc μ-oxo species. Further reduction results in the formation of Mn(II)Pc(− 3) rather than Mn(I)Pc(− 2).
- Full Text:
- Date Issued: 2011
- Authors: Quinton, Damien , Antunes, Edith M , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248450 , vital:51687 , xlink:href="https://doi.org/10.1016/j.inoche.2010.11.029"
- Description: We report here on the synthesis of a new manganese phthalocyanine complex, namely Mn tetrakis(5-hexyn-oxy) phthalocyanine (3), specifically designed to possess an alkyne moiety for its potential use in controlled immobilization on electrodes via the so called “click” chemistry reaction. The electrochemical activity of complex 3 was investigated by cyclic voltammetry and the nature of the observed redox couples was elucidated by spectroelectrochemistry. This work has also shown that the reduction of Mn(III)Pc complex to Mn(II)Pc is accompanied by the formation of MnPc μ-oxo species. Further reduction results in the formation of Mn(II)Pc(− 3) rather than Mn(I)Pc(− 2).
- Full Text:
- Date Issued: 2011
The development of novel nickel selective amine extractants
- Okewole, Adeleye I, Antunes, Edith M, Nyokong, Tebello, Tshentu, Zenixole R
- Authors: Okewole, Adeleye I , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241641 , vital:50957 , xlink:href="https://doi.org/10.1016/j.mineng.2013.04.019"
- Description: A chelating ion exchanger, prepared by functionalising Merrifield resin with 2,2′-pyridylimidazole, was utilized to selectively adsorb and separate nickel from other base metal ions in synthetic sulfate solutions. The sorbent material was characterized by scanning electron microscopy (SEM), microanalysis, infrared (IR), X-ray photoelectron spectroscopy (XPS) and BET surface area. The distribution ratio (D) and the sorption capacity of the microspheres toward Ni(II), Cu(II), Co(II) and Fe(II) ions was studied by using the batch and column methods, respectively. Ni(II) followed by Cu(II) showed the highest distribution ratio (D) and the highest sorption efficiency of nickel(II) ions around pH 2. The binary separation of nickel(II) from copper(II), cobalt(II) and iron(II) respectively, undertaken in a column study, through loading the metal ions at pH ≈ 2 followed by selective decomplexation, demonstrated the selectivity of the sorbent material for nickel(II). Thus, 2,2′-pyridylimidazole can be regarded as a nickel-specific extractant.
- Full Text:
- Date Issued: 2013
- Authors: Okewole, Adeleye I , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241641 , vital:50957 , xlink:href="https://doi.org/10.1016/j.mineng.2013.04.019"
- Description: A chelating ion exchanger, prepared by functionalising Merrifield resin with 2,2′-pyridylimidazole, was utilized to selectively adsorb and separate nickel from other base metal ions in synthetic sulfate solutions. The sorbent material was characterized by scanning electron microscopy (SEM), microanalysis, infrared (IR), X-ray photoelectron spectroscopy (XPS) and BET surface area. The distribution ratio (D) and the sorption capacity of the microspheres toward Ni(II), Cu(II), Co(II) and Fe(II) ions was studied by using the batch and column methods, respectively. Ni(II) followed by Cu(II) showed the highest distribution ratio (D) and the highest sorption efficiency of nickel(II) ions around pH 2. The binary separation of nickel(II) from copper(II), cobalt(II) and iron(II) respectively, undertaken in a column study, through loading the metal ions at pH ≈ 2 followed by selective decomplexation, demonstrated the selectivity of the sorbent material for nickel(II). Thus, 2,2′-pyridylimidazole can be regarded as a nickel-specific extractant.
- Full Text:
- Date Issued: 2013
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
The development of catalytic oxovanadium (IV)-containing microspheres for the oxidation of various organosulfur compounds
- Ogunlaja, Adeniyi S, Khene, Samson M, Antunes, Edith M, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Ogunlaja, Adeniyi S , Khene, Samson M , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241783 , vital:50969 , xlink:href="https://doi.org/10.1016/j.apcata.2013.05.004"
- Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil.
- Full Text:
- Date Issued: 2013
- Authors: Ogunlaja, Adeniyi S , Khene, Samson M , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241783 , vital:50969 , xlink:href="https://doi.org/10.1016/j.apcata.2013.05.004"
- Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil.
- Full Text:
- Date Issued: 2013