Synthesis, photophysics and photochemistry of phthalocyanine-ɛ-polylysine conjugates in the presence of metal nanoparticles against Staphylococcus aureus
- Nombona, Nolwazi, Antunes, Edith M, Chidawanyika, Wadzanai J U, Kleyi, Phumelele, Tshentu, Zenixole R, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Antunes, Edith M , Chidawanyika, Wadzanai J U , Kleyi, Phumelele , Tshentu, Zenixole R , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244439 , vital:51257 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: This work reports on the photodynamic activity of Zn phthalocyanine-ɛ-polylysine conjugates in the presence of gold and silver nanoparticles (NPs) towards the inactivation of Staphylococcus aureus (S. aureus). The conjugates showed high photoinactivation with ∼6% growth at a drug dose of 3 μM and fluence of 39.6 mW/cm2 for 10 min irradiation time in the presence of silver nanoparticles. The presence of silver nanoparticels from the minimal inhibition concentration (MIC50) studies showed remarkable growth inhibition for the tested conjugates even at low concentrations. The MIC50 was lowest for the conjugate of 3 with ɛ-polylysine at concentrations of less than 0.0058 μM in the presence of AgNPs. The lethal photosensitization of microorganisms has emerged as a promising treatment since bacteria have reduced possibilities of developing resistance to photodynamic therapy.
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- Authors: Nombona, Nolwazi , Antunes, Edith M , Chidawanyika, Wadzanai J U , Kleyi, Phumelele , Tshentu, Zenixole R , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244439 , vital:51257 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: This work reports on the photodynamic activity of Zn phthalocyanine-ɛ-polylysine conjugates in the presence of gold and silver nanoparticles (NPs) towards the inactivation of Staphylococcus aureus (S. aureus). The conjugates showed high photoinactivation with ∼6% growth at a drug dose of 3 μM and fluence of 39.6 mW/cm2 for 10 min irradiation time in the presence of silver nanoparticles. The presence of silver nanoparticels from the minimal inhibition concentration (MIC50) studies showed remarkable growth inhibition for the tested conjugates even at low concentrations. The MIC50 was lowest for the conjugate of 3 with ɛ-polylysine at concentrations of less than 0.0058 μM in the presence of AgNPs. The lethal photosensitization of microorganisms has emerged as a promising treatment since bacteria have reduced possibilities of developing resistance to photodynamic therapy.
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The synthesis and characterisation of magnetic nanoparticles and their interaction with a zinc phthalocyanine
- Antunes, Edith M, Rapulenyane, Nomasonto, Ledwaba, Mpho, Litwinski, Christian, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Antunes, Edith M , Rapulenyane, Nomasonto , Ledwaba, Mpho , Litwinski, Christian , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242111 , vital:51002 , xlink:href="https://doi.org/10.1016/j.inoche.2012.12.010"
- Description: A variety of nanoparticles (NPs), including FePt nanoparticles with Fe as the shell (2) or Pt as the shell (3), Pt NPs (4), and FePd (5) were synthesised, characterised and their effect on a zinc phthalocyanine (1) tetra-substituted with a pyridyl-oxy substituent studied using UV/Vis and fluorescence spectroscopy (including time correlated single photon counting, TCSPC). The nanoparticles were characterised using a number of techniques including UV/Vis and inductively coupled plasma-optical emission (ICP-OES) spectroscopies, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and electron paramagnetic resonance (EPR) spectroscopy. Nanocomposites (NCs, 6,7) where the ZnPc (1) was used as the stabiliser, instead of oleic acid and or oleylamine, were also synthesised and characterised.
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- Authors: Antunes, Edith M , Rapulenyane, Nomasonto , Ledwaba, Mpho , Litwinski, Christian , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242111 , vital:51002 , xlink:href="https://doi.org/10.1016/j.inoche.2012.12.010"
- Description: A variety of nanoparticles (NPs), including FePt nanoparticles with Fe as the shell (2) or Pt as the shell (3), Pt NPs (4), and FePd (5) were synthesised, characterised and their effect on a zinc phthalocyanine (1) tetra-substituted with a pyridyl-oxy substituent studied using UV/Vis and fluorescence spectroscopy (including time correlated single photon counting, TCSPC). The nanoparticles were characterised using a number of techniques including UV/Vis and inductively coupled plasma-optical emission (ICP-OES) spectroscopies, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and electron paramagnetic resonance (EPR) spectroscopy. Nanocomposites (NCs, 6,7) where the ZnPc (1) was used as the stabiliser, instead of oleic acid and or oleylamine, were also synthesised and characterised.
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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%.
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- 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%.
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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.
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- 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.
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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.
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- Authors: Ogunlaja, Adeniyi S , Chidawanyika, Wadzanai J U , Antunes, Edith M , Fernandes, Manuel A , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246025 , vital:51429 , xlink:href="https://doi.org/10.1039/C2DT31433A"
- Description: The reaction between [VIVOSO4] and the tetradentate N2O2-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [VIVO(sal-HBPD)]. The molecular structure of [VIVO(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N2O2 binding mode of the tetradentate ligand. The formation of the polymer-supported p[VIVO(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [VIVOSO4]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[VIVO(sal-AHBPD)] were found to be 6.9 m2 g−1 and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[VIVO(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application of this catalyst in the oxidative desulfurization of crude oils.
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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.
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- 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.
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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.
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- 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.
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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.
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- 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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Unquenched fluorescence lifetime for β-phenylthio substituted zinc phthalocyanine upon conjugation to gold nanoparticles
- Forteath, Shaun, Antunes, Edith M, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245774 , vital:51404 , xlink:href="https://doi.org/10.1016/j.poly.2011.12.015"
- Description: Photoinduced processes in phthalocyanine-functionalized gold nanoparticles have been investigated by spectroscopic measurements. The zinc phthalocyanine used contained four phenylthio peripheral substituents (ZnPc(SPh)4). The conjugates formed are represented as ZnPc(SPh)4–AuNP. The absorption spectrum of the ZnPc(SPh)4–AuNP shows a broadening of the phthalocyanine Q-band absorption, probably due to a tight packing of the phthalocyanines on the gold nanoparticle surface. For the attached phthalocyanines, the two fluorescence lifetimes obtained by time-correlated single photon counting (TCSPC) were determined to be both longer and shorter than that of the free Pc. The fluorescence lifetimes were resolved using time resolved fluorescence spectroscopy (TRES).
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- Authors: Forteath, Shaun , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245774 , vital:51404 , xlink:href="https://doi.org/10.1016/j.poly.2011.12.015"
- Description: Photoinduced processes in phthalocyanine-functionalized gold nanoparticles have been investigated by spectroscopic measurements. The zinc phthalocyanine used contained four phenylthio peripheral substituents (ZnPc(SPh)4). The conjugates formed are represented as ZnPc(SPh)4–AuNP. The absorption spectrum of the ZnPc(SPh)4–AuNP shows a broadening of the phthalocyanine Q-band absorption, probably due to a tight packing of the phthalocyanines on the gold nanoparticle surface. For the attached phthalocyanines, the two fluorescence lifetimes obtained by time-correlated single photon counting (TCSPC) were determined to be both longer and shorter than that of the free Pc. The fluorescence lifetimes were resolved using time resolved fluorescence spectroscopy (TRES).
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Photocatalytic behaviour of tantalum (V) phthalocyanines in the presence of gold nanoparticles towards the oxidation of cyclohexene
- Chauke, Vongani P, Antunes, Edith M, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Chauke, Vongani P , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247904 , vital:51628 , xlink:href="https://doi.org/10.1016/j.molcata.2010.11.023"
- Description: This paper presents the photocatalytic oxidation of cyclohexene using (OH)3TaPc derivatives in the absence or presence of gold nanoparticles (AuNPs). The photochemical parameters that include photodegradation (ΦP) and singlet oxygen (ΦΔ) quantum yields are also reported in this work. The ΦΔ values were 0.47 and 0.36 for complexes 1a and 1b, respectively. The ΦΔ values improved drastically in the presence of AuNPs to 0.75 and 0.88, respectively. The ΦP values ranged from 1.02 to 2.45 × 10−6, showing stability of TaPc derivatives in the absence and presence of AuNPs. The photocatalytic products identified using gas chromatograph (GC) are cyclohexene oxide, 2-cyclohexen-1-ol, 2-cyclohexene-1-one and 1,2-cyclohexanediol. The percentage conversion values were higher in the presence of AuNPs. Singlet oxygen was determined to be the main agent involved in the photocatalytic oxidation of cyclohexene. The product yield percentage values for both TaPc complexes (1a and 1b) and TaPc in the presence of AuNPs ranged from 6.3 to 21.2%.
- Full Text:
- Authors: Chauke, Vongani P , Antunes, Edith M , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247904 , vital:51628 , xlink:href="https://doi.org/10.1016/j.molcata.2010.11.023"
- Description: This paper presents the photocatalytic oxidation of cyclohexene using (OH)3TaPc derivatives in the absence or presence of gold nanoparticles (AuNPs). The photochemical parameters that include photodegradation (ΦP) and singlet oxygen (ΦΔ) quantum yields are also reported in this work. The ΦΔ values were 0.47 and 0.36 for complexes 1a and 1b, respectively. The ΦΔ values improved drastically in the presence of AuNPs to 0.75 and 0.88, respectively. The ΦP values ranged from 1.02 to 2.45 × 10−6, showing stability of TaPc derivatives in the absence and presence of AuNPs. The photocatalytic products identified using gas chromatograph (GC) are cyclohexene oxide, 2-cyclohexen-1-ol, 2-cyclohexene-1-one and 1,2-cyclohexanediol. The percentage conversion values were higher in the presence of AuNPs. Singlet oxygen was determined to be the main agent involved in the photocatalytic oxidation of cyclohexene. The product yield percentage values for both TaPc complexes (1a and 1b) and TaPc in the presence of AuNPs ranged from 6.3 to 21.2%.
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Photophysical behaviour of asymmetrically substituted metal free, Mg and Zn phthalocyanines in the presence of folic acid
- Nombona, Nolwazi, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247705 , vital:51608 , xlink:href="https://doi.org/10.1016/j.poly.2010.11.033"
- Description: This work reports on the synthesis, characterisation and photophysical properties of new asymmetric metal free, magnesium and zinc phthalocyanines containing a mono carboxylic acid group for possible linking to biological molecules via an amide bond. Successful synthesis of the phthalocyanines was achieved through the statistical condensation method. The phthalocyanines were mixed with folic acid and their photophysical properties were examined. The triplet quantum yield values for all the complexes in DMSO were between 0.49 and 0.74 and in the presence of folic acid they were between 0.37 and 0.63. The lifetimes were generally good ranging from 70 to 290 μs in the absence or presence of folic acid.
- Full Text:
- Authors: Nombona, Nolwazi , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247705 , vital:51608 , xlink:href="https://doi.org/10.1016/j.poly.2010.11.033"
- Description: This work reports on the synthesis, characterisation and photophysical properties of new asymmetric metal free, magnesium and zinc phthalocyanines containing a mono carboxylic acid group for possible linking to biological molecules via an amide bond. Successful synthesis of the phthalocyanines was achieved through the statistical condensation method. The phthalocyanines were mixed with folic acid and their photophysical properties were examined. The triplet quantum yield values for all the complexes in DMSO were between 0.49 and 0.74 and in the presence of folic acid they were between 0.37 and 0.63. The lifetimes were generally good ranging from 70 to 290 μs in the absence or presence of folic acid.
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The Electrochemical Behavior of Gold Nanoparticle‐Tantalum (V) Phthalocyanine Composites
- Chauke, Vongani, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Chauke, Vongani , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247915 , vital:51629 , xlink:href="https://doi.org/10.1002/elan.201000521"
- Description: The formation of gold nanoparticle (AuNP) composites with tantalum phthalocyanines (TaPc) complexes {1a and 1b (Figure 1)} is reported. The TaPc-AuNPs conjugates were characterised by atomic force microscopy (AFM) and transmission electron microscopy. The AFM analyses show that conjugates of TaPc with AuNPs are more aggregated when compared to AuNPs alone. The conjugates and TaPc complexes were immobilized on a gold electrode by drop and dry method and these were characterized by electrochemical impedance spectroscopy. The charge transfer behaviour of AuNPs was enhanced in the presence of TaPc complexes. All the modified electrodes showed electrocatalytic oxidation of bisphenol A. The limits of detection for complexes 1a and 1b were 4.78×10−10 and 2.76×10−10 mol L−1, respectively.
- Full Text:
- Authors: Chauke, Vongani , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247915 , vital:51629 , xlink:href="https://doi.org/10.1002/elan.201000521"
- Description: The formation of gold nanoparticle (AuNP) composites with tantalum phthalocyanines (TaPc) complexes {1a and 1b (Figure 1)} is reported. The TaPc-AuNPs conjugates were characterised by atomic force microscopy (AFM) and transmission electron microscopy. The AFM analyses show that conjugates of TaPc with AuNPs are more aggregated when compared to AuNPs alone. The conjugates and TaPc complexes were immobilized on a gold electrode by drop and dry method and these were characterized by electrochemical impedance spectroscopy. The charge transfer behaviour of AuNPs was enhanced in the presence of TaPc complexes. All the modified electrodes showed electrocatalytic oxidation of bisphenol A. The limits of detection for complexes 1a and 1b were 4.78×10−10 and 2.76×10−10 mol L−1, respectively.
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Photophysical study of a covalently linked quantum dot–low symmetry phthalocyanine conjugate
- Chidawanyika, Wadzanai J U, Litwinski, Christian, Antunes, Edith M, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Litwinski, Christian , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261641 , vital:53430 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.03.008"
- Description: The linkage of a low symmetry phthalocyanine, ZnttbIPc to mercaptopropionic acid (MPA) capped CdTe quantum dots has been achieved using a coupling agent, dicyclohexylcarbodiimide (DCC), to facilitate formation of an amide bond. UV–vis, Raman and IR spectroscopic studies on the linked (QD:ZnttbIPc-linked) conjugate suggest the reaction was a success. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnttbIPc in both the linked (QD:ZnttbIPc-linked) and mixed (QD:ZnttbIPc-mixed) conjugates. The linked complex (QD:ZnttbIPc-linked) gave the largest FRET efficiency hence showing the advantages of covalent linking. Photophysicochemical properties of the phthalocyanine were improved in the presence of the QDs i.e. for QD:ZnttbIPc-mixed. Fluorescence lifetimes of QDs were unchanged in QD:ZnttbIPc-mixed and decreased for QD:ZnttbIPc-linked.
- Full Text:
- Authors: Chidawanyika, Wadzanai J U , Litwinski, Christian , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261641 , vital:53430 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.03.008"
- Description: The linkage of a low symmetry phthalocyanine, ZnttbIPc to mercaptopropionic acid (MPA) capped CdTe quantum dots has been achieved using a coupling agent, dicyclohexylcarbodiimide (DCC), to facilitate formation of an amide bond. UV–vis, Raman and IR spectroscopic studies on the linked (QD:ZnttbIPc-linked) conjugate suggest the reaction was a success. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnttbIPc in both the linked (QD:ZnttbIPc-linked) and mixed (QD:ZnttbIPc-mixed) conjugates. The linked complex (QD:ZnttbIPc-linked) gave the largest FRET efficiency hence showing the advantages of covalent linking. Photophysicochemical properties of the phthalocyanine were improved in the presence of the QDs i.e. for QD:ZnttbIPc-mixed. Fluorescence lifetimes of QDs were unchanged in QD:ZnttbIPc-mixed and decreased for QD:ZnttbIPc-linked.
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Effect of peripheral fused ring substitution on the optical spectroscopy and electronic structure of metal phthalocyanine complexes
- Chidawanyika, Wadzanai J U, Mack, John, Shimizu, Soji, Kobayashi, Nagao, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Mack, John , Shimizu, Soji , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263353 , vital:53620 , xlink:href="https://doi.org/10.1142/S1088424609001339"
- Description: In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.
- Full Text:
- Authors: Chidawanyika, Wadzanai J U , Mack, John , Shimizu, Soji , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263353 , vital:53620 , xlink:href="https://doi.org/10.1142/S1088424609001339"
- Description: In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.
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Spectroscopic and photophysicochemical behaviour of novel cadmium phthalocyanine derivatives tetra-substituted at the alpha and beta positions
- Nyokong, Tebello, Chidawanyika, Wadzanai J U
- Authors: Nyokong, Tebello , Chidawanyika, Wadzanai J U
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6582 , http://hdl.handle.net/10962/d1004147
- Description: The syntheses of three cadmium phthalocyanine derivatives tetrakis{1,(4)-(4-benzyloxy)phenoxyphthalocyaninato} (5a), tetrakis{1,(4)-(2-pyridyloxy)phthalocyaninato} (5b) and tetrakis{2,(3)-(4-benzyloxy)phenoxyphthalocyaninato} (6a) are reported here for the first time. Spectroscopic and photophysical properties have also been determined and the results are discussed here paying particular attention to the influence of various organic solvents in relation to the position and type of substitution. Singlet oxygen quantum yields (ΦΔ) and photodegradation quantum yields (ΦPd) have also been discussed. The triplet quantum yields have been determined and ranged from ΦT = 0.36 to 0.85, where the peripherally (β) substituted derivatives generally give higher values than those substituted at the non-peripheral (α) positions. The triplet lifetimes ranged from τT = 5 to 40 μs. In all cases (except toluene, due to the lack of data), the highest singlet oxygen quantum yields obtained were for the pyridyloxy-substituted derivatives 5b (ΦΔ = 0.60 in DMF) and 6b (ΦΔ = 0.74 in DMSO).
- Full Text:
- Authors: Nyokong, Tebello , Chidawanyika, Wadzanai J U
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6582 , http://hdl.handle.net/10962/d1004147
- Description: The syntheses of three cadmium phthalocyanine derivatives tetrakis{1,(4)-(4-benzyloxy)phenoxyphthalocyaninato} (5a), tetrakis{1,(4)-(2-pyridyloxy)phthalocyaninato} (5b) and tetrakis{2,(3)-(4-benzyloxy)phenoxyphthalocyaninato} (6a) are reported here for the first time. Spectroscopic and photophysical properties have also been determined and the results are discussed here paying particular attention to the influence of various organic solvents in relation to the position and type of substitution. Singlet oxygen quantum yields (ΦΔ) and photodegradation quantum yields (ΦPd) have also been discussed. The triplet quantum yields have been determined and ranged from ΦT = 0.36 to 0.85, where the peripherally (β) substituted derivatives generally give higher values than those substituted at the non-peripheral (α) positions. The triplet lifetimes ranged from τT = 5 to 40 μs. In all cases (except toluene, due to the lack of data), the highest singlet oxygen quantum yields obtained were for the pyridyloxy-substituted derivatives 5b (ΦΔ = 0.60 in DMF) and 6b (ΦΔ = 0.74 in DMSO).
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The synthesis and photophysicochemical properties of low-symmetry zinc phthalocyanine analogues
- Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263397 , vital:53624 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.06.005"
- Description: The synthesis of a low-symmetry derivative, zinc mono-carboxy substituted phthalocyanine, ZnPc-COOH (4) has been reported. The photochemical and photophysical properties of ZnPc-COOH (4), ZnTMPyPc (5), ZnttbPc (6) and a previously synthesized low-symmetry derivative, ZnttbIPc (7), in various organic solvents are reported. The red-shifting of the spectra of 4 and 5 (relative to that of unsubstituted zinc phthalocyanine, ZnPc) is a function of the electron-donating sulfur-containing substituents attached to the periphery of the molecule. High triplet quantum yields (ФT) generally occur in response to substitution on the zinc phthalocyanine ring periphery. The highest ФT values and triplet lifetimes (τT) occur in DMSO for all derivatives as a result of the solvent's high viscosity. The strongly electron-withdrawing imido fused ring of ZnttbIPc (7) stabilizes it against photo-oxidative degradation relative to the other derivatives.
- Full Text:
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263397 , vital:53624 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.06.005"
- Description: The synthesis of a low-symmetry derivative, zinc mono-carboxy substituted phthalocyanine, ZnPc-COOH (4) has been reported. The photochemical and photophysical properties of ZnPc-COOH (4), ZnTMPyPc (5), ZnttbPc (6) and a previously synthesized low-symmetry derivative, ZnttbIPc (7), in various organic solvents are reported. The red-shifting of the spectra of 4 and 5 (relative to that of unsubstituted zinc phthalocyanine, ZnPc) is a function of the electron-donating sulfur-containing substituents attached to the periphery of the molecule. High triplet quantum yields (ФT) generally occur in response to substitution on the zinc phthalocyanine ring periphery. The highest ФT values and triplet lifetimes (τT) occur in DMSO for all derivatives as a result of the solvent's high viscosity. The strongly electron-withdrawing imido fused ring of ZnttbIPc (7) stabilizes it against photo-oxidative degradation relative to the other derivatives.
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Synthesis and solvent effects on the photophysicochemical properties of novel cadmium phenoxy phthalocyanines
- Chidawanyika, Wadzanai J U, Antunes, Edith M, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Antunes, Edith M , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268649 , vital:54217 , xlink:href="https://doi.org/10.1016/j.jphotochem.2007.09.020"
- Description: The syntheses of novel cadmium phenoxy complexes; tetrakis{1,(4)-tert-butylphenoxyphthalocyaninato}cadmium(II) (5a), tetrakis{1,(4)-phenoxyphthalocyaninato}cadmium(II) (5b), tetrakis{2,(3)-tert-butylphenoxyphthalocyaninato}cadmium(II) (6a) and tetrakis{2,(3)-phenoxyphthalocyaninato}cadmium(II) (6b) are presented herein. The spectroscopic and photophysicochemical properties have also been carried out and discussed together with the influence of various organic solvents on these properties. Spectroscopic properties, i.e. ground state electronic absorption and fluorescence spectra have been found to vary as a function of substituent position on the phthalocyanine macrocycle, i.e. α-substitution versus β-substitution. The photophysical parameters are reported as well as the photodegradation and singlet oxygen quantum yields, where the complexes were found to exhibit good photostability with the production of appreciable amounts of singlet oxygen.
- Full Text:
- Authors: Chidawanyika, Wadzanai J U , Antunes, Edith M , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268649 , vital:54217 , xlink:href="https://doi.org/10.1016/j.jphotochem.2007.09.020"
- Description: The syntheses of novel cadmium phenoxy complexes; tetrakis{1,(4)-tert-butylphenoxyphthalocyaninato}cadmium(II) (5a), tetrakis{1,(4)-phenoxyphthalocyaninato}cadmium(II) (5b), tetrakis{2,(3)-tert-butylphenoxyphthalocyaninato}cadmium(II) (6a) and tetrakis{2,(3)-phenoxyphthalocyaninato}cadmium(II) (6b) are presented herein. The spectroscopic and photophysicochemical properties have also been carried out and discussed together with the influence of various organic solvents on these properties. Spectroscopic properties, i.e. ground state electronic absorption and fluorescence spectra have been found to vary as a function of substituent position on the phthalocyanine macrocycle, i.e. α-substitution versus β-substitution. The photophysical parameters are reported as well as the photodegradation and singlet oxygen quantum yields, where the complexes were found to exhibit good photostability with the production of appreciable amounts of singlet oxygen.
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Syntheses and photophysics of new phthalocyanine derivatives of zinc, cadmium and mercury
- Chidawanyika, Wadzanai J U, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283940 , vital:56005 , xlink:href="https://doi.org/10.1039/B615663K"
- Description: The syntheses of novel tetra{2,(3)-pyridyloxyphthalocyaninato} complexes of zinc, cadmium and mercury (TPyZnPc, TPyCdPc and TPyHgPc) are presented. Their spectral and photophysical properties (as well as those of their unsubstituted counterparts: ZnPc, CdPc and HgPc) are investigated. TPyZnPc and TPyCdPc are aggregated in non-coordinating solvents such as chloroform, while TPyHgPc is demetallated, as evident from their respective absorption spectra. The trends in fluorescence (ΦF), triplet (ΦT) and singlet oxygen (ΦΔ) quantum yields are explained in terms of relative strengths of spin–orbit coupling induced by the respective central metal ions in the complexes. The effect of the pyridyloxy substituents is a decrease in ΦF and an increase in ΦT values. The complexes are less fluorescent in DMSO but possess higher ΦT, triplet lifetimes (τT) and ΦΔ therein.
- Full Text:
- Authors: Chidawanyika, Wadzanai J U , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283940 , vital:56005 , xlink:href="https://doi.org/10.1039/B615663K"
- Description: The syntheses of novel tetra{2,(3)-pyridyloxyphthalocyaninato} complexes of zinc, cadmium and mercury (TPyZnPc, TPyCdPc and TPyHgPc) are presented. Their spectral and photophysical properties (as well as those of their unsubstituted counterparts: ZnPc, CdPc and HgPc) are investigated. TPyZnPc and TPyCdPc are aggregated in non-coordinating solvents such as chloroform, while TPyHgPc is demetallated, as evident from their respective absorption spectra. The trends in fluorescence (ΦF), triplet (ΦT) and singlet oxygen (ΦΔ) quantum yields are explained in terms of relative strengths of spin–orbit coupling induced by the respective central metal ions in the complexes. The effect of the pyridyloxy substituents is a decrease in ΦF and an increase in ΦT values. The complexes are less fluorescent in DMSO but possess higher ΦT, triplet lifetimes (τT) and ΦΔ therein.
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Characterization of amine-functionalized single-walled carbon nanotube-low symmetry phthalocyanine conjugates
- Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7237 , http://hdl.handle.net/10962/d1019688
- Description: Functionalization of single-walled carbon nanotubes (SWCNTs) with amine groups using a previously developed diazonium approach, followed by reaction with a carboxylic acid moiety allows direct attachment by an amide bond. We have developed a new SWCNT-low symmetry phthalocyanine conjugate using this approach, using dicyclohexylcarbodiimide as an activating agent to facilitate formation of an amide bond to give a covalently linked conjugate. A conjugate formed by non-covalent attachment has been used for a comparative investigation by FT-IR, Raman, and UV–Vis spectroscopies, and thermal gravimetric analysis. The fluorescence of the phthalocyanine is quenched in the conjugate. , Original publication is available at http://dx.doi.org/10.1016/j.carbon.2010.04.015
- Full Text: false
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7237 , http://hdl.handle.net/10962/d1019688
- Description: Functionalization of single-walled carbon nanotubes (SWCNTs) with amine groups using a previously developed diazonium approach, followed by reaction with a carboxylic acid moiety allows direct attachment by an amide bond. We have developed a new SWCNT-low symmetry phthalocyanine conjugate using this approach, using dicyclohexylcarbodiimide as an activating agent to facilitate formation of an amide bond to give a covalently linked conjugate. A conjugate formed by non-covalent attachment has been used for a comparative investigation by FT-IR, Raman, and UV–Vis spectroscopies, and thermal gravimetric analysis. The fluorescence of the phthalocyanine is quenched in the conjugate. , Original publication is available at http://dx.doi.org/10.1016/j.carbon.2010.04.015
- Full Text: false
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