Photophysical and nonlinear optical characteristics of pyridyl substituted phthalocyanine-detonation nanodiamond conjugated systems in solution
- Matshitse, Refilwe, Khene, Samson M, Nyokong, Tebello
- Authors: Matshitse, Refilwe , Khene, Samson M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187079 , vital:44563 , xlink:href="https://doi.org/10.1016/j.diamond.2019.03.013"
- Description: In this study photophysical, nonlinear absorption and optical limiting properties of detonation nanodiamonds (DNDs)-phthalocyanine nanoconjugate systems containing: 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyaninato (H2TPPc), 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato zinc(II) (ZnTPPc) and 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato silicon(IV) hydroxide (Si(OH)2TPPc), were investigated in dimethylsulfoxide solution. Pcs were non-covalently linked to nanondiamonds (also covalently linked for Si(OH)2TPPc) and investigated using 532 nm laser excitation at 10 ns pulses for their optical limiting properties. Complexes that have higher triplet state absorption also possessed enhanced nonlinear optical behaviour following reverse saturable absorption mechanism. Superior optical performance is observed when the Pcs had a central metal with axial ligands conjugated to DNDs in solution. Nanoconjugate of DNDs-Si(OH)2TPPc and respective Pc in solution gave the highest imaginary third-order susceptibility (Im[X(3)]) and hyperpolarizability (γ) at 2.91 × 10−8 and 3.17 × 10−8 esu and 3.88 × 10−28 and 4.22 × 10−28 esu, respectively, with Ilim value of 0.47 and 0.39 J·cm−2.
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- Authors: Matshitse, Refilwe , Khene, Samson M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187079 , vital:44563 , xlink:href="https://doi.org/10.1016/j.diamond.2019.03.013"
- Description: In this study photophysical, nonlinear absorption and optical limiting properties of detonation nanodiamonds (DNDs)-phthalocyanine nanoconjugate systems containing: 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyaninato (H2TPPc), 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato zinc(II) (ZnTPPc) and 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato silicon(IV) hydroxide (Si(OH)2TPPc), were investigated in dimethylsulfoxide solution. Pcs were non-covalently linked to nanondiamonds (also covalently linked for Si(OH)2TPPc) and investigated using 532 nm laser excitation at 10 ns pulses for their optical limiting properties. Complexes that have higher triplet state absorption also possessed enhanced nonlinear optical behaviour following reverse saturable absorption mechanism. Superior optical performance is observed when the Pcs had a central metal with axial ligands conjugated to DNDs in solution. Nanoconjugate of DNDs-Si(OH)2TPPc and respective Pc in solution gave the highest imaginary third-order susceptibility (Im[X(3)]) and hyperpolarizability (γ) at 2.91 × 10−8 and 3.17 × 10−8 esu and 3.88 × 10−28 and 4.22 × 10−28 esu, respectively, with Ilim value of 0.47 and 0.39 J·cm−2.
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Photophysical properties and photodynamic therapy activities of detonated nanodiamonds-BODIPY-phthalocyanines nanoassemblies
- Matshitse, Refilwe, Ngoy, Bokolombe P, Managa, Muthumuni, Mack, John, Nyokong, Tebello
- Authors: Matshitse, Refilwe , Ngoy, Bokolombe P , Managa, Muthumuni , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186981 , vital:44553 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.03.007"
- Description: This work reports on the synthesis of nanoassemblies of supramolecular hybrids containing detonated nanodiamonds (DNDs) covalently linked to halogenated BODIPY (DNDs-BODIPY) by an amide bond, followed by π–π stacking of 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) on the DNDs-BODIPY conjugate, to form nanoassembly represented as ZnTPPcQ-DNDs-BODIPY. ZnTPPcQ-DNDs-BODIPY has a higher singlet oxygen quantum yield of 0.50 in water. Therefore, the construction of a three component photodynamic therapy agent (ZnTPPcQ-DNDs-BODIPY) as a single photosentisiser improved singlet quantum yields of the Pc. Zeta potential studies of ZnTPPcQ-DNDs-BODIPY under various temperatures, concentrations and pH conditions, showed the conjugate is more stable at pHs 2, 4 and 7 and at high concentrations (50 μg/mL) and temperatures (80 °C). ZnTPPcQ-DNDs-BODIPY showed high photodynamic therapy (PDT) activity with a low MCF-7 cell viability of 21 ± 5% when compared to 31 ± 2%, 30 ± 2% and 28 ± 2% cell viability at the highest tested concentration of 50 μg/mL for DNDs, ZnTPPcQ-DND and DNDs-BODIPY, respectively.
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- Authors: Matshitse, Refilwe , Ngoy, Bokolombe P , Managa, Muthumuni , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186981 , vital:44553 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.03.007"
- Description: This work reports on the synthesis of nanoassemblies of supramolecular hybrids containing detonated nanodiamonds (DNDs) covalently linked to halogenated BODIPY (DNDs-BODIPY) by an amide bond, followed by π–π stacking of 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) on the DNDs-BODIPY conjugate, to form nanoassembly represented as ZnTPPcQ-DNDs-BODIPY. ZnTPPcQ-DNDs-BODIPY has a higher singlet oxygen quantum yield of 0.50 in water. Therefore, the construction of a three component photodynamic therapy agent (ZnTPPcQ-DNDs-BODIPY) as a single photosentisiser improved singlet quantum yields of the Pc. Zeta potential studies of ZnTPPcQ-DNDs-BODIPY under various temperatures, concentrations and pH conditions, showed the conjugate is more stable at pHs 2, 4 and 7 and at high concentrations (50 μg/mL) and temperatures (80 °C). ZnTPPcQ-DNDs-BODIPY showed high photodynamic therapy (PDT) activity with a low MCF-7 cell viability of 21 ± 5% when compared to 31 ± 2%, 30 ± 2% and 28 ± 2% cell viability at the highest tested concentration of 50 μg/mL for DNDs, ZnTPPcQ-DND and DNDs-BODIPY, respectively.
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Photophysical properties and photodynamic therapy activities of symmetrical and asymmetrical porphyrins embedded into Pluronic polymer micelles and nonlinear optical properties of an asymmetrical phthalocyanine
- Authors: Managa, Muthumuni Elizabeth
- Date: 2019
- Subjects: Porphyrins , Phthalocyanines
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/67625 , vital:29122
- Description: This work reports on the synthesis of symmetrical and asymmetrical novel porphyrins that have been incorporated into Pluronic polymers, as well as the synthesis of asymmetrical phthalocyanine. The new compounds were characterized by elemental analysis, Fourier-transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (1H NMR), mass spectrometry and UV–Visible spectroscopy. The porphyrins that are synthesised were not water soluble but upon incorporating into Pluronic polymer micelles, they became water soluble. The polymer was also modified and linked to folic acid, to enhance selectivity for photodynamic therapy application, where MCF7 breast cancer cells were used. The singlet oxygen quantum yields were lower for the metal free porphyrins as compared to metalled ones due to the heavy atom effect of ClGa, Zn and Cl2Si in the latter which encourages intersystem crossing to the triplet state. Singlet oxygen quantum yields for water soluble derivatives increased upon being encapsulated into the micelles for all. The Stern-Volmer constant (Ksv), binding constant (Kb) and number of binding sites (n) were investigated in order to understand the interaction between the polymer micelles and the porphyrins, and it was showed that the central metals play a role in the manner which the porphyrin interacts with the micelles. The dark toxicity and photodynamic activity of the novel porphyrins upon encapsulating to Pluronic polymer micelles is also reported. There was minimal dark toxicity for all complexes with > 90% cell survival. The photodynamic activity of water insoluble porphyrins improved when encapsulated into the micelles. Novel asymmetrical phthalocyanines were also synthesised for nonlinear optics (NLO) studies in solution and thin films.
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- Authors: Managa, Muthumuni Elizabeth
- Date: 2019
- Subjects: Porphyrins , Phthalocyanines
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/67625 , vital:29122
- Description: This work reports on the synthesis of symmetrical and asymmetrical novel porphyrins that have been incorporated into Pluronic polymers, as well as the synthesis of asymmetrical phthalocyanine. The new compounds were characterized by elemental analysis, Fourier-transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (1H NMR), mass spectrometry and UV–Visible spectroscopy. The porphyrins that are synthesised were not water soluble but upon incorporating into Pluronic polymer micelles, they became water soluble. The polymer was also modified and linked to folic acid, to enhance selectivity for photodynamic therapy application, where MCF7 breast cancer cells were used. The singlet oxygen quantum yields were lower for the metal free porphyrins as compared to metalled ones due to the heavy atom effect of ClGa, Zn and Cl2Si in the latter which encourages intersystem crossing to the triplet state. Singlet oxygen quantum yields for water soluble derivatives increased upon being encapsulated into the micelles for all. The Stern-Volmer constant (Ksv), binding constant (Kb) and number of binding sites (n) were investigated in order to understand the interaction between the polymer micelles and the porphyrins, and it was showed that the central metals play a role in the manner which the porphyrin interacts with the micelles. The dark toxicity and photodynamic activity of the novel porphyrins upon encapsulating to Pluronic polymer micelles is also reported. There was minimal dark toxicity for all complexes with > 90% cell survival. The photodynamic activity of water insoluble porphyrins improved when encapsulated into the micelles. Novel asymmetrical phthalocyanines were also synthesised for nonlinear optics (NLO) studies in solution and thin films.
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Photophysical properties and photodynamic therapy activity of a meso-tetra (4-carboxyphenyl) porphyrin tetramethyl ester–graphene quantum dot conjugate
- Managa, Muthumuni, Ngoy, Bokolombe P, Nyokong, Tebello
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187533 , vital:44669 , xlink:href="https://doi.org/10.1039/C8NJ06175K"
- Description: Novel meso-tetra(4-carboxyphenyl)porphyrin tetramethyl ester metal derivatives were synthesised and characterized. These derivatives were interacted with graphene quantum dots (GDQs). Spectroscopic evidence that was obtained showed that the resultant conjugates were stable due to the strong π–π stacking interaction between the GQDs and the porphyrins. The fluorescence and singlet oxygen generating behaviour of the porphyrins and the nanoconjugates were investigated following incorporation. The dark toxicity and photodynamic therapy activities of the porphyrins and the nanoconjugates were successfully studied using MCF-7 breast cancer cells. Cell viability for the dark toxicity was more than 90% for all complexes. The PDT activities at the highest concentration of 120 μg ml−1 showed a decrease in cell viability down to 15.2% for the GaClTMPP–GQDs.
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- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187533 , vital:44669 , xlink:href="https://doi.org/10.1039/C8NJ06175K"
- Description: Novel meso-tetra(4-carboxyphenyl)porphyrin tetramethyl ester metal derivatives were synthesised and characterized. These derivatives were interacted with graphene quantum dots (GDQs). Spectroscopic evidence that was obtained showed that the resultant conjugates were stable due to the strong π–π stacking interaction between the GQDs and the porphyrins. The fluorescence and singlet oxygen generating behaviour of the porphyrins and the nanoconjugates were investigated following incorporation. The dark toxicity and photodynamic therapy activities of the porphyrins and the nanoconjugates were successfully studied using MCF-7 breast cancer cells. Cell viability for the dark toxicity was more than 90% for all complexes. The PDT activities at the highest concentration of 120 μg ml−1 showed a decrease in cell viability down to 15.2% for the GaClTMPP–GQDs.
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Photophysicochemical and photodynamic therapy properties of metallophthalocyanines linked to gold speckled silica nanoparticles
- Dube, Edith, Oluwole, David O, Niemuwa, Nwaji, Prinsloo, Earl, Nyokong, Tebello
- Authors: Dube, Edith , Oluwole, David O , Niemuwa, Nwaji , Prinsloo, Earl , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187472 , vital:44657 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.01.019"
- Description: This work reports on the linkage of 2(3),9(10),16(17),23(24) tetrakis [(benzo[d]thiazol-2-yl phenoxy) phthalocyaninato] zinc(II) (1) and indium(III) chloride (2) to gold speckled silica (GSS) nanoparticles via gold to sulphur (Au-S) and gold to nitrogen (Au-N) self-assembly to form the conjugates: 1-GSS and 2-GSS. The formed conjugates were characterized using microscopic and spectroscopic techniques, and the photophysicochemical properties and photodynamic therapy (PDT) activity against human breast adenocarcinoma cell line (MCF-7 cells) were studied. The conjugates afforded decrease in fluorescence quantum yields with corresponding increase in triplet and singlet oxygen quantum yields when compared to phthalocyanines alone. Singlet oxygen is cytotoxic to cancer cells hence it is important for PDT. The in vitro dark toxicity of complex 2 and 2-GSS against MCF–7 cells showed ≥93% viable cells within concentration ranges of 10–160 μg/mL. 2–GSS showed enhanced PDT activity with less than 50% viable cells at 80 μg/mL as compared to 2 and GSS alone which showed > 60% viable cells within 10–160 μg/mL. The observed improvements in the PDT activity of 2-GSS could be attributed to the high singlet oxygen generation of 2-GSS compared to 2 alone in addition to the phototoxicity of GSS.
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- Authors: Dube, Edith , Oluwole, David O , Niemuwa, Nwaji , Prinsloo, Earl , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187472 , vital:44657 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.01.019"
- Description: This work reports on the linkage of 2(3),9(10),16(17),23(24) tetrakis [(benzo[d]thiazol-2-yl phenoxy) phthalocyaninato] zinc(II) (1) and indium(III) chloride (2) to gold speckled silica (GSS) nanoparticles via gold to sulphur (Au-S) and gold to nitrogen (Au-N) self-assembly to form the conjugates: 1-GSS and 2-GSS. The formed conjugates were characterized using microscopic and spectroscopic techniques, and the photophysicochemical properties and photodynamic therapy (PDT) activity against human breast adenocarcinoma cell line (MCF-7 cells) were studied. The conjugates afforded decrease in fluorescence quantum yields with corresponding increase in triplet and singlet oxygen quantum yields when compared to phthalocyanines alone. Singlet oxygen is cytotoxic to cancer cells hence it is important for PDT. The in vitro dark toxicity of complex 2 and 2-GSS against MCF–7 cells showed ≥93% viable cells within concentration ranges of 10–160 μg/mL. 2–GSS showed enhanced PDT activity with less than 50% viable cells at 80 μg/mL as compared to 2 and GSS alone which showed > 60% viable cells within 10–160 μg/mL. The observed improvements in the PDT activity of 2-GSS could be attributed to the high singlet oxygen generation of 2-GSS compared to 2 alone in addition to the phototoxicity of GSS.
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Photophysicochemical properties and surface-enhanced Raman scattering of phthalocyanine-nanoparticle conjugates
- Authors: Nwahara, Nnamdi
- Date: 2019
- Subjects: Boron compounds , Electrochemistry , Phthalocyanines , Nanoparticles , Bioconjugates , Raman effect
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/71647 , vital:29928
- Description: This work presents the synthesis, photophysical and photochemical characterization of a series of metallophthalocyanines (MPcs) and boron dipyrromethene (BODIPY) and their conjugates with either gold or silver nanoparticles (AuNPs or AgNPs) or graphene quantum dots (GQDs). The rich π-electron systems of GQDs and MPcs employed in this work enabled the coordination of MPcs to GQDs (either as pristine or modified) via the non-covalent (π-π stacking) method. GQDs, AuNPs and AgNPs were also functionalized with L-glutathione (GSH) in order to assist coupling to the Pcs or BODIPY dye. Spectroscopic and microscopic studies confirmed the formation of the respective nanoparticles (NPs) as well as the conjugates which exhibited enhanced photophysicochemical properties in comparison to the phthalocyanines (Pcs) or BODIPY alone. This work also shows that the incorporation of folic acid (FA) into Pcs-NPs composites leads to further enhancements in the singlet oxygen generation capabilities of the resulting conjugates, and so experimentally demonstrates for the first time, a synergy between FA and the respective nanoparticles (GQDs, AuNPs and AgNPs) in affecting the photophysical properties of Pcs complexes. GQDs and Pcs/GQDs hybrids were also herein decorated with AuNPs – metallic nanostructures that employ localized surface plasmon resonances to capture or radiate electromagnetic waves at optical frequencies. These nanostructures herein reported, have been shown to possess enhanced light-matter properties, enabling unique surface-enhanced Raman scattering (SERS) behaviours, with unprecedented enhancement factors of up to 30-fold. This work therefore, reports on the fabrication of Pc/GQDs/AuNPs hybrids and experimentally demonstrates their incredible potential as novel Raman-active PDT agents.
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- Authors: Nwahara, Nnamdi
- Date: 2019
- Subjects: Boron compounds , Electrochemistry , Phthalocyanines , Nanoparticles , Bioconjugates , Raman effect
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/71647 , vital:29928
- Description: This work presents the synthesis, photophysical and photochemical characterization of a series of metallophthalocyanines (MPcs) and boron dipyrromethene (BODIPY) and their conjugates with either gold or silver nanoparticles (AuNPs or AgNPs) or graphene quantum dots (GQDs). The rich π-electron systems of GQDs and MPcs employed in this work enabled the coordination of MPcs to GQDs (either as pristine or modified) via the non-covalent (π-π stacking) method. GQDs, AuNPs and AgNPs were also functionalized with L-glutathione (GSH) in order to assist coupling to the Pcs or BODIPY dye. Spectroscopic and microscopic studies confirmed the formation of the respective nanoparticles (NPs) as well as the conjugates which exhibited enhanced photophysicochemical properties in comparison to the phthalocyanines (Pcs) or BODIPY alone. This work also shows that the incorporation of folic acid (FA) into Pcs-NPs composites leads to further enhancements in the singlet oxygen generation capabilities of the resulting conjugates, and so experimentally demonstrates for the first time, a synergy between FA and the respective nanoparticles (GQDs, AuNPs and AgNPs) in affecting the photophysical properties of Pcs complexes. GQDs and Pcs/GQDs hybrids were also herein decorated with AuNPs – metallic nanostructures that employ localized surface plasmon resonances to capture or radiate electromagnetic waves at optical frequencies. These nanostructures herein reported, have been shown to possess enhanced light-matter properties, enabling unique surface-enhanced Raman scattering (SERS) behaviours, with unprecedented enhancement factors of up to 30-fold. This work therefore, reports on the fabrication of Pc/GQDs/AuNPs hybrids and experimentally demonstrates their incredible potential as novel Raman-active PDT agents.
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Physicochemical and antimicrobial photodynamic chemotherapy (against E. coli) by indium phthalocyanines in the presence of silver–iron bimetallic nanoparticles
- Magadla, Aviwe, Oluwole, David O, Managa, Muthumuni, Nyokong, Tebello
- Authors: Magadla, Aviwe , Oluwole, David O , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187091 , vital:44564 , xlink:href="https://doi.org/10.1016/j.poly.2019.01.032"
- Description: In this work, Schiff base indium phthalocyanines: In–Cl tetrakis N,N-dimethyl-4-(methylimino) phthalocyanine (complex 1b) and In–Cl tetrakis phenoxy N,N-dimethyl-4-(methylimino) phthalocyanine (complex 2b) are synthesized from tetra amino and tetra phenoxy amino phthalocyanines, respectively. These complexes were further quartenised with 1,3-propanesultone to form zwitterionic complexes 1 and 2, respectively. Silver–iron dimers (Ag–Fe3O4) and silver-iron core shell (Ag@Fe3O4) nanoparticles (NPs) were linked to the synthesised complexes. The photophysical and photochemical behaviour of the complexes and their conjugates with NPs were investigated in dimethyl sulfoxide. Complexes 2 and 2b and their conjugates were then used for photodynamic antimicrobial chemotherapy on Escherichia coli. The zwitter ionic photosensitiser 2 and its conjugates showed better efficiency for photodynamic antimicrobial chemotherapy compared to their neutral counterparts.
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- Authors: Magadla, Aviwe , Oluwole, David O , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187091 , vital:44564 , xlink:href="https://doi.org/10.1016/j.poly.2019.01.032"
- Description: In this work, Schiff base indium phthalocyanines: In–Cl tetrakis N,N-dimethyl-4-(methylimino) phthalocyanine (complex 1b) and In–Cl tetrakis phenoxy N,N-dimethyl-4-(methylimino) phthalocyanine (complex 2b) are synthesized from tetra amino and tetra phenoxy amino phthalocyanines, respectively. These complexes were further quartenised with 1,3-propanesultone to form zwitterionic complexes 1 and 2, respectively. Silver–iron dimers (Ag–Fe3O4) and silver-iron core shell (Ag@Fe3O4) nanoparticles (NPs) were linked to the synthesised complexes. The photophysical and photochemical behaviour of the complexes and their conjugates with NPs were investigated in dimethyl sulfoxide. Complexes 2 and 2b and their conjugates were then used for photodynamic antimicrobial chemotherapy on Escherichia coli. The zwitter ionic photosensitiser 2 and its conjugates showed better efficiency for photodynamic antimicrobial chemotherapy compared to their neutral counterparts.
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Physicochemical and photodynamic antimicrobial chemotherapy activity of morpholine-substituted phthalocyanines: Effect of point of substitution and central metal
- Sindelo, Azole, Kobayashi, Nagao, Kimura, Mutsumi, Nyokong, Tebello
- Authors: Sindelo, Azole , Kobayashi, Nagao , Kimura, Mutsumi , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187438 , vital:44652 , xlink:href="https://doi.org/10.1016/j.jphotochem.2019.01.025"
- Description: In this study, novel metal-free, zinc and indium 1(4),8(11),15(18),22(25)-tetramorpholine (1a, 2a, 3a respectively) and 2(3), 9(10), 16(17),23(24)-tetramorpholine (1b, 2b, 3b respectively) phthalocyanines were synthesized and complexes 2 and 3 were quaternized. The photophysical and photochemical properties were investigated in dimethylsulfoxide. The non-peripherally substituted phthalocyanines generated higher singlet oxygen than the peripherally substituted phthalocyanines. Photodynamic antimicrobial chemotherapy activities towards inactivation of Escherichia coli, Staphylococcus aureus and Candida albican were evaluated, where all the quaternized Pcs showed total elimination of the micro-organism with log reductions greater than 9. Though the neutral Pcs had log reductions less than 2, for C. albican the percentage reduction was 68.5% for 2b showing the antifungal properties of the morpholine group.
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- Authors: Sindelo, Azole , Kobayashi, Nagao , Kimura, Mutsumi , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187438 , vital:44652 , xlink:href="https://doi.org/10.1016/j.jphotochem.2019.01.025"
- Description: In this study, novel metal-free, zinc and indium 1(4),8(11),15(18),22(25)-tetramorpholine (1a, 2a, 3a respectively) and 2(3), 9(10), 16(17),23(24)-tetramorpholine (1b, 2b, 3b respectively) phthalocyanines were synthesized and complexes 2 and 3 were quaternized. The photophysical and photochemical properties were investigated in dimethylsulfoxide. The non-peripherally substituted phthalocyanines generated higher singlet oxygen than the peripherally substituted phthalocyanines. Photodynamic antimicrobial chemotherapy activities towards inactivation of Escherichia coli, Staphylococcus aureus and Candida albican were evaluated, where all the quaternized Pcs showed total elimination of the micro-organism with log reductions greater than 9. Though the neutral Pcs had log reductions less than 2, for C. albican the percentage reduction was 68.5% for 2b showing the antifungal properties of the morpholine group.
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Physicochemical properties and photodynamic therapy activities of indium and zinc phthalocyanine-nanoparticle conjugates
- Authors: Dube, Edith
- Date: 2019
- Subjects: Indium , Zinc , Phthalocyanines , Breast -- Cancer -- Photochemotherapy , Nanoparticles
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/76506 , vital:30589
- Description: The syntheses and characterization of symmetric and asymmetric Pcs functionalized at the peripheral position are reported. The Pcs contain either zinc or indium as central metals and have carboxyphenoxy, phenoxy propanoic acid, benzothiazole phenoxy, thiophine ethoxy or di-O-isopropylidene-α-D-glucopyranose as ring substituents. The Pcs were linked to NPs via an amide bond or through self-assembly. The photophysics and photochemistry of the Pcs were assessed when alone and with conjugates. All the studied Pcs showed good photophysicochemical behaviour with relatively high triplet and singlet oxygen quantum yields corresponding to their low fluorescence quantum yield. The Pcs with indium in their central cavity exhibited higher triplet and singlet oxygen quantum yields in comparison to their zinc counterparts due to the heavy–atom effect obtained from the former. Asymmetrical Pcs displayed higher triplet and singlet oxygen quantum yields than their symmetrical counterparts. The triplet quantum yield, generally increased on linkage to nanoparticles (NPs) due to the heavy–atom effect of gold and silver in NPs. The conjugates to gold nanospheres yielded higher triplet and singlet quantum yields than their gold nanotriangles counterparts due to the higher loading by the former probably encouraged by their relatively small particle size. The in vitro dark cytotoxicity and photodynamic therapy of selected Pc complexes and conjugates against MCF-7 cells was tested. All studied Pc complexes and conjugates showed minimum dark toxicity making them applicable for PDT. All complexes displayed poor phototoxicity with >50Îll viability at concentrations≤ 160μg/mL, however the conjugates showed<50% cell viabilityatconcentrations≤ 160μg/mLprobably due to the enhanced singlet oxygen quantum yield. The findings from this work show the importance of linking photosensitises such as phthalocyanines to metal nanoparticles for the enhancement ofsinglet oxygen quantum yield and ultimately the photodynamic effect.
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- Authors: Dube, Edith
- Date: 2019
- Subjects: Indium , Zinc , Phthalocyanines , Breast -- Cancer -- Photochemotherapy , Nanoparticles
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/76506 , vital:30589
- Description: The syntheses and characterization of symmetric and asymmetric Pcs functionalized at the peripheral position are reported. The Pcs contain either zinc or indium as central metals and have carboxyphenoxy, phenoxy propanoic acid, benzothiazole phenoxy, thiophine ethoxy or di-O-isopropylidene-α-D-glucopyranose as ring substituents. The Pcs were linked to NPs via an amide bond or through self-assembly. The photophysics and photochemistry of the Pcs were assessed when alone and with conjugates. All the studied Pcs showed good photophysicochemical behaviour with relatively high triplet and singlet oxygen quantum yields corresponding to their low fluorescence quantum yield. The Pcs with indium in their central cavity exhibited higher triplet and singlet oxygen quantum yields in comparison to their zinc counterparts due to the heavy–atom effect obtained from the former. Asymmetrical Pcs displayed higher triplet and singlet oxygen quantum yields than their symmetrical counterparts. The triplet quantum yield, generally increased on linkage to nanoparticles (NPs) due to the heavy–atom effect of gold and silver in NPs. The conjugates to gold nanospheres yielded higher triplet and singlet quantum yields than their gold nanotriangles counterparts due to the higher loading by the former probably encouraged by their relatively small particle size. The in vitro dark cytotoxicity and photodynamic therapy of selected Pc complexes and conjugates against MCF-7 cells was tested. All studied Pc complexes and conjugates showed minimum dark toxicity making them applicable for PDT. All complexes displayed poor phototoxicity with >50Îll viability at concentrations≤ 160μg/mL, however the conjugates showed<50% cell viabilityatconcentrations≤ 160μg/mLprobably due to the enhanced singlet oxygen quantum yield. The findings from this work show the importance of linking photosensitises such as phthalocyanines to metal nanoparticles for the enhancement ofsinglet oxygen quantum yield and ultimately the photodynamic effect.
- Full Text:
Phytochemical, anti-inflammatory and anti-trypanosomal properties of Anthocleista vogelii Planch (Loganiaceae) stem bark
- Eze, Fabian I, Siwe-Noundou, Xavier, Osadebe, Patience, Krause, Rui W M
- Authors: Eze, Fabian I , Siwe-Noundou, Xavier , Osadebe, Patience , Krause, Rui W M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/194059 , vital:45419 , xlink:href="https://doi.org/10.1016/j.jep.2019.111851"
- Description: Ethnopharmacological relevance: Anthocleista vogelii Planch (Loganiaceae) is used in African Traditional Medicine for the treatment of pain and inflammatory disorders as well as sleeping sickness. Aim of the study: To determine the in vivo anti-inflammatory and in vitro anti-trypanosomal activities of the extracts of A. vogelii stem bark and identify the phytochemical classes of the fractions responsible for the activities. Materials and methods: The in vivo anti-inflammatory activity of the extracts was evaluated using the egg albumin-induced rat paw oedema model while the in vitro anti-trypanosomal activity was assessed on Trypanosoma brucei brucei. The in vitro cytotoxicity was assessed on HeLa (human cervix adenocarcinoma) cell line. Results: The methanolic extract of A. vogelii stem bark, with 11.2% yield, gave LD50 > 5000 mg/kg. The n-hexane fraction of the extract contains steroids, terpenes and fatty acids and yielded non-cytotoxic terpenoidal column fraction with anti-trypanosomal IC50 of 3.0 μg/mL. The ethylacetate fraction at 100 mg/kg dose significantly (p less than 0.05) provoked 37.8, 62.5 and 69.7% inhibition of oedema induced by egg-albumin at the second, fourth and sixth hours respectively. Conclusion: The study demonstrated that the anti-inflammatory and anti-trypanosomal activities of A. vogelii are probably due to non-cytotoxic terpenoids and validated the traditional use of A. vogelii in the treatment of inflammation and sleeping sickness.
- Full Text:
- Authors: Eze, Fabian I , Siwe-Noundou, Xavier , Osadebe, Patience , Krause, Rui W M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/194059 , vital:45419 , xlink:href="https://doi.org/10.1016/j.jep.2019.111851"
- Description: Ethnopharmacological relevance: Anthocleista vogelii Planch (Loganiaceae) is used in African Traditional Medicine for the treatment of pain and inflammatory disorders as well as sleeping sickness. Aim of the study: To determine the in vivo anti-inflammatory and in vitro anti-trypanosomal activities of the extracts of A. vogelii stem bark and identify the phytochemical classes of the fractions responsible for the activities. Materials and methods: The in vivo anti-inflammatory activity of the extracts was evaluated using the egg albumin-induced rat paw oedema model while the in vitro anti-trypanosomal activity was assessed on Trypanosoma brucei brucei. The in vitro cytotoxicity was assessed on HeLa (human cervix adenocarcinoma) cell line. Results: The methanolic extract of A. vogelii stem bark, with 11.2% yield, gave LD50 > 5000 mg/kg. The n-hexane fraction of the extract contains steroids, terpenes and fatty acids and yielded non-cytotoxic terpenoidal column fraction with anti-trypanosomal IC50 of 3.0 μg/mL. The ethylacetate fraction at 100 mg/kg dose significantly (p less than 0.05) provoked 37.8, 62.5 and 69.7% inhibition of oedema induced by egg-albumin at the second, fourth and sixth hours respectively. Conclusion: The study demonstrated that the anti-inflammatory and anti-trypanosomal activities of A. vogelii are probably due to non-cytotoxic terpenoids and validated the traditional use of A. vogelii in the treatment of inflammation and sleeping sickness.
- Full Text:
Pigs vs people: the use of pigs as analogues for humans in forensic entomology and taphonomy research
- Matuszewski, Szymon, Hall, Martin J R, Moreau, Gaétan, Schoenly, Kenneth G, Tarone, Aaron M, Villet, Martin H
- Authors: Matuszewski, Szymon , Hall, Martin J R , Moreau, Gaétan , Schoenly, Kenneth G , Tarone, Aaron M , Villet, Martin H
- Date: 2019
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/140557 , vital:37898 , DOI: 10.1007/s00414-019-02074-5
- Description: Most studies of decomposition in forensic entomology and taphonomy have used non-human cadavers. Following the recommendation of using domestic pig cadavers as analogues for humans in forensic entomology in the 1980s, pigs became the most frequently used model cadavers in forensic sciences. They have shaped our understanding of how large vertebrate cadavers decompose in, for example, various environments, seasons and after various ante- or postmortem cadaver modifications. They have also been used to demonstrate the feasibility of several new or well-established forensic techniques. The advent of outdoor human taphonomy facilities enabled experimental comparisons of decomposition between pig and human cadavers. Recent comparisons challenged the pig-as-analogue claim in entomology and taphonomy research. In this review, we discuss in a broad methodological context the advantages and disadvantages of pig and human cadavers for forensic research and rebut the critique of pigs as analogues for humans. We conclude that experiments using human cadaver analogues (i.e. pig carcasses) are easier to replicate and more practical for controlling confounding factors than studies based solely on humans and, therefore, are likely to remain our primary epistemic source of forensic knowledge for the immediate future. We supplement these considerations with new guidelines for model cadaver choice in forensic science research.
- Full Text:
- Authors: Matuszewski, Szymon , Hall, Martin J R , Moreau, Gaétan , Schoenly, Kenneth G , Tarone, Aaron M , Villet, Martin H
- Date: 2019
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/140557 , vital:37898 , DOI: 10.1007/s00414-019-02074-5
- Description: Most studies of decomposition in forensic entomology and taphonomy have used non-human cadavers. Following the recommendation of using domestic pig cadavers as analogues for humans in forensic entomology in the 1980s, pigs became the most frequently used model cadavers in forensic sciences. They have shaped our understanding of how large vertebrate cadavers decompose in, for example, various environments, seasons and after various ante- or postmortem cadaver modifications. They have also been used to demonstrate the feasibility of several new or well-established forensic techniques. The advent of outdoor human taphonomy facilities enabled experimental comparisons of decomposition between pig and human cadavers. Recent comparisons challenged the pig-as-analogue claim in entomology and taphonomy research. In this review, we discuss in a broad methodological context the advantages and disadvantages of pig and human cadavers for forensic research and rebut the critique of pigs as analogues for humans. We conclude that experiments using human cadaver analogues (i.e. pig carcasses) are easier to replicate and more practical for controlling confounding factors than studies based solely on humans and, therefore, are likely to remain our primary epistemic source of forensic knowledge for the immediate future. We supplement these considerations with new guidelines for model cadaver choice in forensic science research.
- Full Text:
Plants, people, and place: complex, mutualistic, and co-evolving global patterns through time
- Authors: Van Wijk, Yvette Ethné
- Date: 2019
- Subjects: Ethnobotany -- South Africa -- Western Cape , Khoisan (African people) -- Ethnobotany , Human-plant relationships -- South Africa -- Western Cape , Plants -- Classification -- South Africa -- Western Cape , Plant remains (Archaeology) -- South Africa -- Western Cape , Ethnoscience -- South Africa -- Western Cape , Regression analysis
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/76575 , vital:30609
- Description: My thesis studies and analyses the suite of distinctive plant taxa which persist in small patches of vegetation growing in close association with archaeological habitation sites in the southern Cape, South Africa. The unexpected correlation and overlap between botanical taxa collected at 75 site complexes, and ethnobotanical data collected in collaboration with modern Khoi-San communities in the same area, is explored and interrogated. Although sparse, reports of the same suite of taxa recovered from archaeological excavations in the Cape provinces provides depth of time to the study, linking the past to the present. The three-way correlation of a suite of plants closely associated with humans and habitation sites through time, allows for triangulation of the data in order to validate and cross verify the results using more than one frame of reference. Both the plants and the knowledge about their uses have persisted in spite of historical attrition, and alienation of land and language, suffered by the Khoi-San over the past 300 years. Drawing on a large body of primary and secondary data, and using an interdisciplinary, abductive and pragmatic mixed methods approach, a pattern can be traced throughout Africa and globally. Regression analysis strongly indicates that the most ubiquitous taxa were selected for a purpose and are not randomly present in association with humans. Botanical, anthropological, and archaeological studies seldom focus on the inter-connectedness of people and plants at the sites they inhabited. Very little research into modern vegetation in close association with the sites has been undertaken, and vegetation mapping has not captured the occurrence of these site-specific small vegetation patches recorded during my surveys. The topographically, geologically, and vegetatively complex and varied southern Cape, and greater Cape area, is extremely rich in archaeological sites and history. This study suggests that the value of site-specific plant taxa to humans throughout the aeons of pre-agricultural history, persists into the present. Due to tolerance of a broad range of climatic and environmental variables, there is value in the study of these ancient and neglected useful plants in the face of climate change. That this vegetation is so closely associated with archaeological sites of cultural and historic importance confers an urgency to recognising the existence and significance of the distinctive and possibly anthropogenic vegetation surrounding the sites.
- Full Text:
- Authors: Van Wijk, Yvette Ethné
- Date: 2019
- Subjects: Ethnobotany -- South Africa -- Western Cape , Khoisan (African people) -- Ethnobotany , Human-plant relationships -- South Africa -- Western Cape , Plants -- Classification -- South Africa -- Western Cape , Plant remains (Archaeology) -- South Africa -- Western Cape , Ethnoscience -- South Africa -- Western Cape , Regression analysis
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/76575 , vital:30609
- Description: My thesis studies and analyses the suite of distinctive plant taxa which persist in small patches of vegetation growing in close association with archaeological habitation sites in the southern Cape, South Africa. The unexpected correlation and overlap between botanical taxa collected at 75 site complexes, and ethnobotanical data collected in collaboration with modern Khoi-San communities in the same area, is explored and interrogated. Although sparse, reports of the same suite of taxa recovered from archaeological excavations in the Cape provinces provides depth of time to the study, linking the past to the present. The three-way correlation of a suite of plants closely associated with humans and habitation sites through time, allows for triangulation of the data in order to validate and cross verify the results using more than one frame of reference. Both the plants and the knowledge about their uses have persisted in spite of historical attrition, and alienation of land and language, suffered by the Khoi-San over the past 300 years. Drawing on a large body of primary and secondary data, and using an interdisciplinary, abductive and pragmatic mixed methods approach, a pattern can be traced throughout Africa and globally. Regression analysis strongly indicates that the most ubiquitous taxa were selected for a purpose and are not randomly present in association with humans. Botanical, anthropological, and archaeological studies seldom focus on the inter-connectedness of people and plants at the sites they inhabited. Very little research into modern vegetation in close association with the sites has been undertaken, and vegetation mapping has not captured the occurrence of these site-specific small vegetation patches recorded during my surveys. The topographically, geologically, and vegetatively complex and varied southern Cape, and greater Cape area, is extremely rich in archaeological sites and history. This study suggests that the value of site-specific plant taxa to humans throughout the aeons of pre-agricultural history, persists into the present. Due to tolerance of a broad range of climatic and environmental variables, there is value in the study of these ancient and neglected useful plants in the face of climate change. That this vegetation is so closely associated with archaeological sites of cultural and historic importance confers an urgency to recognising the existence and significance of the distinctive and possibly anthropogenic vegetation surrounding the sites.
- Full Text:
Plaxenone A and B: Cytotoxic halogenated monoterpenes from the South African red seaweed Plocamium maxillosum
- Knott, Michael G, de la Mare, Jo-Anne, Edkins, Adrienne L, Zhang, Angel, Stillman, Martin J, Bolton, John J, Antunes, Edith M, Beukes, Denzil R
- Authors: Knott, Michael G , de la Mare, Jo-Anne , Edkins, Adrienne L , Zhang, Angel , Stillman, Martin J , Bolton, John J , Antunes, Edith M , Beukes, Denzil R
- Date: 2019
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/164446 , vital:41119 , https://doi.org/10.1016/j.phytol.2018.12.009
- Description: The endemic South African red seaweed Plocamium maxillosum (Poiret) Lamouroux produces two unusual isomeric dichlorinated cyclohexenone monoterpenes, plaxenone A and B (1 and 2). The structures of the isolated compounds were determined from spectroscopic data and their absolute configuration was determined by comparison of the experimental and calculated ECD spectra. Compounds 1 and 2 inhibit the growth of MDA-MB-231 breast cancer cells.
- Full Text:
- Authors: Knott, Michael G , de la Mare, Jo-Anne , Edkins, Adrienne L , Zhang, Angel , Stillman, Martin J , Bolton, John J , Antunes, Edith M , Beukes, Denzil R
- Date: 2019
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/164446 , vital:41119 , https://doi.org/10.1016/j.phytol.2018.12.009
- Description: The endemic South African red seaweed Plocamium maxillosum (Poiret) Lamouroux produces two unusual isomeric dichlorinated cyclohexenone monoterpenes, plaxenone A and B (1 and 2). The structures of the isolated compounds were determined from spectroscopic data and their absolute configuration was determined by comparison of the experimental and calculated ECD spectra. Compounds 1 and 2 inhibit the growth of MDA-MB-231 breast cancer cells.
- Full Text:
Political constellations: an analysis of the use of language in positioning South African political parties in the Daily Sun
- Authors: Siebörger, Ian
- Date: 2019
- Subjects: Knowledge, Theory of , Political culture South Africa , Systemic grammar , Political parties South Africa , Functionalism (Linguistics) , Mass media and language South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/113934 , vital:33846 , http://doi.org/10.21504/10962/113934
- Description: As a young democracy, post-apartheid South Africa has both a complex and rapidly changing political landscape, and a developing system of interconnected public spheres in which ordinary citizens engage in political discourses. In this context, this thesis examines the ways in which language is used to position South Africa's political parties in the Daily Sun, the country's most widely-read tabloid newspaper. It uses a complex, multi-stage method of analysis to develop tools for describing how different policy positions and moral evaluations are associated with political parties. This is accomplished through complementary analyses using Systemic Functional Linguistics (SFL) and Legitimation Code Theory (LCT). The study describes current political discourses in South Africa as the products of a long process of historical development extending through the segregationist and apartheid eras to the post-apartheid present. It also situates the Daily Sun within South Africa's current media landscape and argues that the newspaper is to some extent successful in facilitating a vibrant alternative public sphere in which readers engage with the news. The study's multi-stage method of analysis begins with a corpus analysis of all political news articles from the Daily Sun dating from January to June 2015. This analysis reveals various tendencies in the positioning of South Africa's three largest political parties that are investigated further in later stages of analysis. Three selected individual articles are subjected to _ne-grained analysis in an exploratory analysis stage, and three others in a targeted analysis stage. The exploratory analyses are designed to investigate the contribution of various linguistic and discursive resources to political positioning in the data, while the targeted analyses demonstrate the contribution of these resources to positioning in articles that were carefully selected to reflect as many of the trends found in the corpus analysis as possible. These analyses enact the concept of axiological-semantic density from LCT to show the ways in which political knowledge is condensed in the articles. This condensation produces constellations of people, policy positions and moral evaluations in each article. These constellations, in turn, give indications of the cosmologies, or organizing principles, behind the Daily Sun's political news coverage. On the basis of the exploratory analyses, a multi-level translation device for axiological-semantic density is developed to describe the ways in which this concept is enacted in the analysis. The use of this translation device is then demonstrated using the targeted analyses. This study adapts the concepts of iconization, aggregation and technicality from SFL, collectively referred to as 'mass', to show how language works to position political parties. It finds that the use of intertextual references and lexical strings makes a considerable contribution toward political positioning in the data. Repeated couplings of the abovementioned resources in complexes (also known as syndromes) drive the process of political positioning. The Daily Sun is found to report primarily on concrete actions by individual politicians, and contains little to no information on policy decisions. No one political party is favoured, but coverage tends to emphasize accusations against politicians. This may reinforce distrust in politics and a withdrawal from engagement in political processes among readers. By contrast, this study shows that engagement in South Africa's public discourses can be encouraged through stronger promotion of critical language awareness in education, the growth of civil society organizations as vehicles for dialogue and social action on matters of public interest, and a variety of initiatives by the media designed to show the relevance of policy decisions to individuals' lives and increase participation in the news-making process. , Thesis (PhD) -- Faculty of Humanities, English Language and Linguistics, 2019
- Full Text: false
- Authors: Siebörger, Ian
- Date: 2019
- Subjects: Knowledge, Theory of , Political culture South Africa , Systemic grammar , Political parties South Africa , Functionalism (Linguistics) , Mass media and language South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/113934 , vital:33846 , http://doi.org/10.21504/10962/113934
- Description: As a young democracy, post-apartheid South Africa has both a complex and rapidly changing political landscape, and a developing system of interconnected public spheres in which ordinary citizens engage in political discourses. In this context, this thesis examines the ways in which language is used to position South Africa's political parties in the Daily Sun, the country's most widely-read tabloid newspaper. It uses a complex, multi-stage method of analysis to develop tools for describing how different policy positions and moral evaluations are associated with political parties. This is accomplished through complementary analyses using Systemic Functional Linguistics (SFL) and Legitimation Code Theory (LCT). The study describes current political discourses in South Africa as the products of a long process of historical development extending through the segregationist and apartheid eras to the post-apartheid present. It also situates the Daily Sun within South Africa's current media landscape and argues that the newspaper is to some extent successful in facilitating a vibrant alternative public sphere in which readers engage with the news. The study's multi-stage method of analysis begins with a corpus analysis of all political news articles from the Daily Sun dating from January to June 2015. This analysis reveals various tendencies in the positioning of South Africa's three largest political parties that are investigated further in later stages of analysis. Three selected individual articles are subjected to _ne-grained analysis in an exploratory analysis stage, and three others in a targeted analysis stage. The exploratory analyses are designed to investigate the contribution of various linguistic and discursive resources to political positioning in the data, while the targeted analyses demonstrate the contribution of these resources to positioning in articles that were carefully selected to reflect as many of the trends found in the corpus analysis as possible. These analyses enact the concept of axiological-semantic density from LCT to show the ways in which political knowledge is condensed in the articles. This condensation produces constellations of people, policy positions and moral evaluations in each article. These constellations, in turn, give indications of the cosmologies, or organizing principles, behind the Daily Sun's political news coverage. On the basis of the exploratory analyses, a multi-level translation device for axiological-semantic density is developed to describe the ways in which this concept is enacted in the analysis. The use of this translation device is then demonstrated using the targeted analyses. This study adapts the concepts of iconization, aggregation and technicality from SFL, collectively referred to as 'mass', to show how language works to position political parties. It finds that the use of intertextual references and lexical strings makes a considerable contribution toward political positioning in the data. Repeated couplings of the abovementioned resources in complexes (also known as syndromes) drive the process of political positioning. The Daily Sun is found to report primarily on concrete actions by individual politicians, and contains little to no information on policy decisions. No one political party is favoured, but coverage tends to emphasize accusations against politicians. This may reinforce distrust in politics and a withdrawal from engagement in political processes among readers. By contrast, this study shows that engagement in South Africa's public discourses can be encouraged through stronger promotion of critical language awareness in education, the growth of civil society organizations as vehicles for dialogue and social action on matters of public interest, and a variety of initiatives by the media designed to show the relevance of policy decisions to individuals' lives and increase participation in the news-making process. , Thesis (PhD) -- Faculty of Humanities, English Language and Linguistics, 2019
- Full Text: false
Popular politics in the rural Western Cape, South Africa: a case study of Ruiterbos
- Authors: Ghedi Alasow, Jonis
- Date: 2019
- Subjects: Political participation -- South Africa -- Cape Town , South Africa -- Politics and government -- 1994- , Land tenure -- Political aspects -- South Africa , Land use, Rural -- Political aspects -- South Africa
- Language: English
- Type: text , Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10962/96165 , vital:31246
- Description: This thesis argues that the philosophical foundations upon which human beings have been engaged have, across various schools of thought, made the mistake of presuming that some people are more modern than others. This suggestion is refuted throughout this thesis. To do this, intellectual traditions that take the fundamental rationality of all human beings as an indispensable starting point are engaged to argue for the need to acknowledge that everyone in the ‘now’ is indeed, of the ‘now’. This thesis connects these debates about modernity, rationality and humanity to the contemporary discussions around rural politics with particular reference to Ruiterbos in the Western Cape province of South Africa. By means of detailed empirical and ethnographic research, this thesis illustrates the issues around which people in Ruiterbos are politicised. Via this case study, the a priori assumption that rural politics will necessarily manifest itself only with respect to questions of land and agrarian reform or labour relations is complicated. The two issues around which people in Ruiterbos, during the time of this research, seem to be politicised – housing and education – are surfaced throughout this thesis. The thesis argues that the findings in this case study call for an expansion of the issues that are traditionally considered when the question of rural politics is raised. The often historicist approach that limits the possibilities for politics in rural areas should be suspended for an approach that takes popular politics and political agents in rural areas seriously. The thesis finally argues that the conclusions that are reached with respect to questions of modernity and rural politics ought to be adopted to allow for more detailed and thorough explanations of popular politics in places like Ruiterbos.
- Full Text:
- Authors: Ghedi Alasow, Jonis
- Date: 2019
- Subjects: Political participation -- South Africa -- Cape Town , South Africa -- Politics and government -- 1994- , Land tenure -- Political aspects -- South Africa , Land use, Rural -- Political aspects -- South Africa
- Language: English
- Type: text , Thesis , Masters , MA
- Identifier: http://hdl.handle.net/10962/96165 , vital:31246
- Description: This thesis argues that the philosophical foundations upon which human beings have been engaged have, across various schools of thought, made the mistake of presuming that some people are more modern than others. This suggestion is refuted throughout this thesis. To do this, intellectual traditions that take the fundamental rationality of all human beings as an indispensable starting point are engaged to argue for the need to acknowledge that everyone in the ‘now’ is indeed, of the ‘now’. This thesis connects these debates about modernity, rationality and humanity to the contemporary discussions around rural politics with particular reference to Ruiterbos in the Western Cape province of South Africa. By means of detailed empirical and ethnographic research, this thesis illustrates the issues around which people in Ruiterbos are politicised. Via this case study, the a priori assumption that rural politics will necessarily manifest itself only with respect to questions of land and agrarian reform or labour relations is complicated. The two issues around which people in Ruiterbos, during the time of this research, seem to be politicised – housing and education – are surfaced throughout this thesis. The thesis argues that the findings in this case study call for an expansion of the issues that are traditionally considered when the question of rural politics is raised. The often historicist approach that limits the possibilities for politics in rural areas should be suspended for an approach that takes popular politics and political agents in rural areas seriously. The thesis finally argues that the conclusions that are reached with respect to questions of modernity and rural politics ought to be adopted to allow for more detailed and thorough explanations of popular politics in places like Ruiterbos.
- Full Text:
Post-release evaluation of Megamelus scutellaris Berg. (hemiptera: delphacidae): a biological control agent of water hyacinth Eichhornia crassipes (Mart.) Solms-Laub (Pontederiaceae) in South Africa
- Authors: Miller, Benjamin Erich
- Date: 2019
- Subjects: Megamelus scutellaris Berg. , Delphacidae , Noxious weeds -- Biological control -- South Africa , Aquatic weeds -- Biological control -- South Africa , Water hyacinth -- Biological control -- South Africa , Biological pest control agents
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/92330 , vital:30710
- Description: Water hyacinth, Eichhornia crassipes (Mart.) Solms-Laub. (Pontederiaceae) is a free-floating aquatic macrophyte from South America that was introduced to South Africa in the 1900s for its attractive ornamental flowers. The plant was classified as a serious invader in the country in the 1970s, eventually becoming the worst invasive aquatic plant in South Africa. Biological control is widely regarded as the most effective method of managing water hyacinth, as it is ecologically safe, cost-effective, and self-sustaining. To date, nine biological control agents have been released in South Africa against water hyacinth, including eight arthropods and a pathogen. Due to the cumulative effects of highly eutrophic waterbodies, which mitigate the damage caused by biological control, and the cold winters which inhibit the rate of biological control agent population build up, South Africa currently has more biological control agents released on water hyacinth than anywhere else in the world. The need for a cold-tolerant agent that can reproduce and develop quickly, while still being damaging to water hyacinth in eutrophic systems, led to the introduction of the most recently released water hyacinth biological control agent, the planthopper Megamelus scutellaris Berg (Hemiptera: Delphacidae), which was initially collected from Argentina. This thesis formed the first post-release evaluation of M. scutellaris since its release in South Africa in 2013. It included a greenhouse experiment to measure the agent’s feeding damage in relation to different nutrient levels and stocking rates, as well as a field component to evaluate both the post-winter recovery of M. scutellaris, and a nationwide survey to measure the establishment of the agent around the country in relation to climate, water quality, and plant health. In the greenhouse experiment, the feeding damage was quantified using measurements of plant growth parameters and chlorophyll fluorometry. It was found that, like other biological control agents of water hyacinth, M. scutellaris was most damaging when released in high numbers on plants grown at medium nutrient levels, and less effective on plants grown at elevated nutrient levels. A water hyacinth infestation on the Kubusi River was selected for the evaluation of the post-winter recovery of M. scutellaris. The Kubusi River is both the first site where M. scutellaris was released, and the coldest site where water hyacinth biological control agents have established successfully in South Africa. Monthly visits tracking seasonal plant health characteristics and agent population densities indicated that the populations of M. scutellaris were impacted most significantly by the season. Low temperatures led to the water hyacinth plants being of poor quality during the winter, which had a subsequent negative effect on the agent populations. The agents could only fully recover by late summer, which meant that the plants were without any significant biological control through the initial phases of the growing season, when they were most vulnerable, and a significant lag-phase occurred between the recovery of the plants and the recovery of the agent population after the winter bottleneck. A survey of all sites where M. scutellaris had been released in South Africa yielded 16 sites where the agents had successfully established, having survived at least one full winter. Among these sites were four sites where the agents were found without them having been released, indicating that they can disperse unaided to new sites. The temperature was a major factor responsible for the success or failure of establishment, with very few agents surviving in the hot areas of South Africa or in areas with a high frost incidence. The density of M. scutellaris was higher in nutrient-rich water, and on plants with more leaves, suggesting that the quality of the plants also contributed to establishment. The results of this thesis showed that M. scutellaris is able to establish successfully in South Africa, and that the agents are capable of causing significant damage to water hyacinth, making it a promising addition to the biological control programme. Novel methods of measuring subtle insect feeding damage in plants and quantifying agent populations are also discussed, along with suggestions for the future implementation of M. scutellaris in South Africa.
- Full Text:
- Authors: Miller, Benjamin Erich
- Date: 2019
- Subjects: Megamelus scutellaris Berg. , Delphacidae , Noxious weeds -- Biological control -- South Africa , Aquatic weeds -- Biological control -- South Africa , Water hyacinth -- Biological control -- South Africa , Biological pest control agents
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/92330 , vital:30710
- Description: Water hyacinth, Eichhornia crassipes (Mart.) Solms-Laub. (Pontederiaceae) is a free-floating aquatic macrophyte from South America that was introduced to South Africa in the 1900s for its attractive ornamental flowers. The plant was classified as a serious invader in the country in the 1970s, eventually becoming the worst invasive aquatic plant in South Africa. Biological control is widely regarded as the most effective method of managing water hyacinth, as it is ecologically safe, cost-effective, and self-sustaining. To date, nine biological control agents have been released in South Africa against water hyacinth, including eight arthropods and a pathogen. Due to the cumulative effects of highly eutrophic waterbodies, which mitigate the damage caused by biological control, and the cold winters which inhibit the rate of biological control agent population build up, South Africa currently has more biological control agents released on water hyacinth than anywhere else in the world. The need for a cold-tolerant agent that can reproduce and develop quickly, while still being damaging to water hyacinth in eutrophic systems, led to the introduction of the most recently released water hyacinth biological control agent, the planthopper Megamelus scutellaris Berg (Hemiptera: Delphacidae), which was initially collected from Argentina. This thesis formed the first post-release evaluation of M. scutellaris since its release in South Africa in 2013. It included a greenhouse experiment to measure the agent’s feeding damage in relation to different nutrient levels and stocking rates, as well as a field component to evaluate both the post-winter recovery of M. scutellaris, and a nationwide survey to measure the establishment of the agent around the country in relation to climate, water quality, and plant health. In the greenhouse experiment, the feeding damage was quantified using measurements of plant growth parameters and chlorophyll fluorometry. It was found that, like other biological control agents of water hyacinth, M. scutellaris was most damaging when released in high numbers on plants grown at medium nutrient levels, and less effective on plants grown at elevated nutrient levels. A water hyacinth infestation on the Kubusi River was selected for the evaluation of the post-winter recovery of M. scutellaris. The Kubusi River is both the first site where M. scutellaris was released, and the coldest site where water hyacinth biological control agents have established successfully in South Africa. Monthly visits tracking seasonal plant health characteristics and agent population densities indicated that the populations of M. scutellaris were impacted most significantly by the season. Low temperatures led to the water hyacinth plants being of poor quality during the winter, which had a subsequent negative effect on the agent populations. The agents could only fully recover by late summer, which meant that the plants were without any significant biological control through the initial phases of the growing season, when they were most vulnerable, and a significant lag-phase occurred between the recovery of the plants and the recovery of the agent population after the winter bottleneck. A survey of all sites where M. scutellaris had been released in South Africa yielded 16 sites where the agents had successfully established, having survived at least one full winter. Among these sites were four sites where the agents were found without them having been released, indicating that they can disperse unaided to new sites. The temperature was a major factor responsible for the success or failure of establishment, with very few agents surviving in the hot areas of South Africa or in areas with a high frost incidence. The density of M. scutellaris was higher in nutrient-rich water, and on plants with more leaves, suggesting that the quality of the plants also contributed to establishment. The results of this thesis showed that M. scutellaris is able to establish successfully in South Africa, and that the agents are capable of causing significant damage to water hyacinth, making it a promising addition to the biological control programme. Novel methods of measuring subtle insect feeding damage in plants and quantifying agent populations are also discussed, along with suggestions for the future implementation of M. scutellaris in South Africa.
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Poverty reduction strategies and non-timber forest products
- Pullanikkatil, Deepa, Shackleton, Charlie M
- Authors: Pullanikkatil, Deepa , Shackleton, Charlie M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , book chapter
- Identifier: http://hdl.handle.net/10962/433583 , vital:72985 , ISBN 978-3-319-75580-9 , https://link.springer.com/chapter/10.1007/978-3-319-75580-9_1
- Description: The first of the 17 Global Goals that make up the 2030 Agenda for Sustainable Development is to end poverty in all its forms everywhere. Although the numbers of poor people in the world has declined over the last few decades, it is still alarmingly high, being approximately 770 million in 2013 (Fig. 1) (World Bank in Understanding Poverty 2017). Currently the majority of the world’s poor live in rural areas, and their livelihoods are dominated by land-based activities including gathering of Non-Timber Forest Products (NTFPs). There were rela tively few studies offering more socially orientated perspectives and insights on the links between NTFP use, dependency and poverty. The ordinary people using NTFPs, their reasons for doing so and their experiences are given in this book.
- Full Text:
- Authors: Pullanikkatil, Deepa , Shackleton, Charlie M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , book chapter
- Identifier: http://hdl.handle.net/10962/433583 , vital:72985 , ISBN 978-3-319-75580-9 , https://link.springer.com/chapter/10.1007/978-3-319-75580-9_1
- Description: The first of the 17 Global Goals that make up the 2030 Agenda for Sustainable Development is to end poverty in all its forms everywhere. Although the numbers of poor people in the world has declined over the last few decades, it is still alarmingly high, being approximately 770 million in 2013 (Fig. 1) (World Bank in Understanding Poverty 2017). Currently the majority of the world’s poor live in rural areas, and their livelihoods are dominated by land-based activities including gathering of Non-Timber Forest Products (NTFPs). There were rela tively few studies offering more socially orientated perspectives and insights on the links between NTFP use, dependency and poverty. The ordinary people using NTFPs, their reasons for doing so and their experiences are given in this book.
- Full Text:
Poverty reduction through non-timber forest products
- Pullanikkatil, Deepa, Shackleton, Charlie M
- Authors: Pullanikkatil, Deepa , Shackleton, Charlie M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/433598 , vital:72986 , ISBN 978-3-319-75580-9 , https://doi.org/10.1007/978-3-319-75580-9
- Description: This book narrates personal stories of people from around the world who have used natural products, in particular Non Timber Forest Products (NTFPs) as a means to come out of poverty. Ending poverty remains a major worldwide challenge and is the number one goal under the UN Sustainable Development Goals. The book fills an important knowledge gap; that of personal stories of NTFP users. This has not been part of past publications on NTFPs which tend to focus on statistics and analysis of numbers, thus, the human faces of NTFP users are missing. Narrative stories provide a wealth of data about people and their experiences rather than aggregated classifications, categories and characteristics of poverty. The objective of this book is to illustrate the poverty alleviation potential of NTFPs through documenting the personal life stories of individuals and households that lifted themselves out of poverty through trade of NTFPs. This book is for all who are interested in poverty alleviation and NTFPs.
- Full Text:
- Authors: Pullanikkatil, Deepa , Shackleton, Charlie M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/433598 , vital:72986 , ISBN 978-3-319-75580-9 , https://doi.org/10.1007/978-3-319-75580-9
- Description: This book narrates personal stories of people from around the world who have used natural products, in particular Non Timber Forest Products (NTFPs) as a means to come out of poverty. Ending poverty remains a major worldwide challenge and is the number one goal under the UN Sustainable Development Goals. The book fills an important knowledge gap; that of personal stories of NTFP users. This has not been part of past publications on NTFPs which tend to focus on statistics and analysis of numbers, thus, the human faces of NTFP users are missing. Narrative stories provide a wealth of data about people and their experiences rather than aggregated classifications, categories and characteristics of poverty. The objective of this book is to illustrate the poverty alleviation potential of NTFPs through documenting the personal life stories of individuals and households that lifted themselves out of poverty through trade of NTFPs. This book is for all who are interested in poverty alleviation and NTFPs.
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Pregnancy Decision Making: Abortion and Adoption
- Mavuso, Jabulile M-J J, Macleod, Catriona I
- Authors: Mavuso, Jabulile M-J J , Macleod, Catriona I
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , book chapter
- Identifier: http://hdl.handle.net/10962/434145 , vital:73034 , ISBN 9781119161899 , https://onlinelibrary.wiley.com/doi/book/10.1002/9781119171492
- Description: Pregnancy decision making encompasses a large range of interactions, including decisions and actions to avoid pregnancy or to become pregnant. This entry addresses the question of decision making regarding the outcome of a pregnancy: abortion or taking the pregnancy to term, with the latter resulting in parenting or adoption placement. Adolescents' pregnancy decision making has been a special area of focus for some decades now, particularly regarding whether adolescents are capable of making termination-of-pregnancy decisions. This entry highlights controversies concerning, first, teenage pregnancy as a social problem; second, risk research that seeks to outline the consequences of various reproductive decisions; third, questions around adolescents' maturity regarding making reproductive decisions; fourth, the reasons provided for various reproductive decisions; and, finally, issues surrounding the autonomy of young pregnant women in their reproductive decisions.
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- Authors: Mavuso, Jabulile M-J J , Macleod, Catriona I
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , book chapter
- Identifier: http://hdl.handle.net/10962/434145 , vital:73034 , ISBN 9781119161899 , https://onlinelibrary.wiley.com/doi/book/10.1002/9781119171492
- Description: Pregnancy decision making encompasses a large range of interactions, including decisions and actions to avoid pregnancy or to become pregnant. This entry addresses the question of decision making regarding the outcome of a pregnancy: abortion or taking the pregnancy to term, with the latter resulting in parenting or adoption placement. Adolescents' pregnancy decision making has been a special area of focus for some decades now, particularly regarding whether adolescents are capable of making termination-of-pregnancy decisions. This entry highlights controversies concerning, first, teenage pregnancy as a social problem; second, risk research that seeks to outline the consequences of various reproductive decisions; third, questions around adolescents' maturity regarding making reproductive decisions; fourth, the reasons provided for various reproductive decisions; and, finally, issues surrounding the autonomy of young pregnant women in their reproductive decisions.
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Preparation of NIR absorbing axial substituted tin (iv) porphyrins and their photocytotoxic properties
- Babu, Balaji, Amuhaya, Edith K, Oluwole, David O, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Amuhaya, Edith K , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234592 , vital:50211 , xlink:href="https://doi.org/10.1039/C8MD00373D"
- Description: Sn(IV) porphyrins ([Sn(IV)TTP(3PyO)2] (5) and [Sn(IV)TPP(3PyO)2] (6) [tetrathienylporphyrin (TTP), tetraphenylporphyrin (TPP), and pyridyloxy (PyO)]) were prepared and characterized and their photocytotoxicity upon irradiation with 625 nm light has been studied. The presence of the 3PyO axial ligands was found to limit the aggregation and enhance the solubility of 5 and 6 in DMF/H2O (1 : 1). The photophysical properties and photodynamic therapy (PDT) activity of the meso-2-thienyl and meso-phenyl-substituted Sn(IV) porphyrins are compared. 5 and 6 were found to be photocytotoxic in MCF-7 cancer cells when irradiated with a Thorlabs M625L3 LED at 625 nm but remained nontoxic in the dark. The PDT activity of Sn(IV) meso-tetra-2-thienylporphyrin 5 was found to be significantly enhanced relative to its analogous tetraphenylporphyrin 6. There is a marked red-shift of the Q00 band of 5 into the therapeutic window due to the meso-2-thienyl rings, and 5 has an unusually high singlet oxygen quantum yield value of 0.83 in DMF. The results demonstrate that readily synthesized axially ligated Sn(IV) meso-arylporphyrins are potentially suitable for use as singlet oxygen photosensitizers in biomedical applications and merit further in depth investigation in this context.
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- Authors: Babu, Balaji , Amuhaya, Edith K , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234592 , vital:50211 , xlink:href="https://doi.org/10.1039/C8MD00373D"
- Description: Sn(IV) porphyrins ([Sn(IV)TTP(3PyO)2] (5) and [Sn(IV)TPP(3PyO)2] (6) [tetrathienylporphyrin (TTP), tetraphenylporphyrin (TPP), and pyridyloxy (PyO)]) were prepared and characterized and their photocytotoxicity upon irradiation with 625 nm light has been studied. The presence of the 3PyO axial ligands was found to limit the aggregation and enhance the solubility of 5 and 6 in DMF/H2O (1 : 1). The photophysical properties and photodynamic therapy (PDT) activity of the meso-2-thienyl and meso-phenyl-substituted Sn(IV) porphyrins are compared. 5 and 6 were found to be photocytotoxic in MCF-7 cancer cells when irradiated with a Thorlabs M625L3 LED at 625 nm but remained nontoxic in the dark. The PDT activity of Sn(IV) meso-tetra-2-thienylporphyrin 5 was found to be significantly enhanced relative to its analogous tetraphenylporphyrin 6. There is a marked red-shift of the Q00 band of 5 into the therapeutic window due to the meso-2-thienyl rings, and 5 has an unusually high singlet oxygen quantum yield value of 0.83 in DMF. The results demonstrate that readily synthesized axially ligated Sn(IV) meso-arylporphyrins are potentially suitable for use as singlet oxygen photosensitizers in biomedical applications and merit further in depth investigation in this context.
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