Synthesis, photophysicochemical properties and photodynamic therapy activities of indium and zinc phthalocyanines when incorporated into Pluronic polymer micelles
- Authors: Motloung, Banele Mike
- Date: 2020
- Subjects: Indium , Zinc , Phthalocyanines , Polymers , Photochemotherapy , Micelles
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167529 , vital:41489
- Description: This thesis reports on the syntheses, photophysicochemical properties and photodynamic therapy activities of symmetrical metallophthalocyanines (MPcs) when alone or when incorporated into Pluronic polymer micelles. The Pcs contain either zinc or indium as central metals and have phenyldiazenylphenoxy, pyridine-2-yloxy and benzo[d]thiazol-2-ylthio as ring substituents. Spectroscopic and microscopic techniques were used to confirm the formation MPcs with micelles. The photophysics and photochemistry of the Pcs were assessed when alone and with micelles. All the studied Pcs showed good photophysicochemical behavior with relatively high triplet and singlet oxygen quantum yields corresponding to their low fluorescence quantum yields. 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. The in vitro dark cytotoxicity and photodynamic therapy of the Pc complexes and conjugates against MCF7 cells was tested. All studied Pc complexes alone and with micelles showed minimum dark toxicity making them applicable for PDT. All complexes displayed good phototoxicity < 50% cell viability (except for complex 2 > 50% cell viability) at concentrations ≤100 μg/mL, however the conjugates showed < 45% cell viability at concentrations ≤ 100 μg/mL, probably due to the small micellar size and EPR effect. The findings from this work show the importance of incorporating photosensitizers such as phthalocyanines into Pluronic polymers micelles and making them water soluble and ultimately improving their photodynamic effect.
- Full Text:
- Date Issued: 2020
- Authors: Motloung, Banele Mike
- Date: 2020
- Subjects: Indium , Zinc , Phthalocyanines , Polymers , Photochemotherapy , Micelles
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/167529 , vital:41489
- Description: This thesis reports on the syntheses, photophysicochemical properties and photodynamic therapy activities of symmetrical metallophthalocyanines (MPcs) when alone or when incorporated into Pluronic polymer micelles. The Pcs contain either zinc or indium as central metals and have phenyldiazenylphenoxy, pyridine-2-yloxy and benzo[d]thiazol-2-ylthio as ring substituents. Spectroscopic and microscopic techniques were used to confirm the formation MPcs with micelles. The photophysics and photochemistry of the Pcs were assessed when alone and with micelles. All the studied Pcs showed good photophysicochemical behavior with relatively high triplet and singlet oxygen quantum yields corresponding to their low fluorescence quantum yields. 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. The in vitro dark cytotoxicity and photodynamic therapy of the Pc complexes and conjugates against MCF7 cells was tested. All studied Pc complexes alone and with micelles showed minimum dark toxicity making them applicable for PDT. All complexes displayed good phototoxicity < 50% cell viability (except for complex 2 > 50% cell viability) at concentrations ≤100 μg/mL, however the conjugates showed < 45% cell viability at concentrations ≤ 100 μg/mL, probably due to the small micellar size and EPR effect. The findings from this work show the importance of incorporating photosensitizers such as phthalocyanines into Pluronic polymers micelles and making them water soluble and ultimately improving their photodynamic effect.
- Full Text:
- Date Issued: 2020
Micellar-enhanced ultrafiltration of palladium and platinum anions
- Authors: Gwicana, Sakumzi
- Date: 2007
- Subjects: Micelles , Ultrafiltration , Palladium catalysts
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10414 , http://hdl.handle.net/10948/518 , Micelles , Ultrafiltration , Palladium catalysts
- Description: The project was concerned with studying the capability of a micellar-enhanced ultrafiltration system (MEUF) to remove platinum group metal ions namely Pt (lV) and Pd (ll) chloro anions from aqueous industrial waste effluents. South Africa has the world’s largest reserves of platinum group metals (PGMs) and other valuable metals such as manganese, chrome ores, titanium minerals etc. which are required for new automotive and other technologies, including fuel cells, catalytic converters and lighter components. The consistent loss with the industrial waste stream and the toxicological effects of these precious metals led to the need to develop new and effective methods to recover them from industrial waste effluents. With such a wide variety of fields where these PGMs are used and the failure of the traditional techniques namely sedimentation, fermentation etc. to effectively reduce or recover these highly toxic and precious metal ions prior to discharging industrial waste effluents, it is necessary to explore other techniques such as membrane technology that can be used to recover these valuable species from industrial waste streams. The present study involved the use of a cationic surfactant, viz cetylpyridinium chloride, which was introduced into an aqueous solution containing palladium and platinum metal anions. The surfactant forms charged micelles above a certain critical concentration value. The metal anions adsorb onto the available oppositely charged sites on the micelle surfaces and are then able to be retained by a suitable membrane. Hollow fibre ultrafiltration membranes with the MWCO of +/- 10 kD and +/-30nm pore size were used as a filter component in this study. For this MEUF system to be effective, it was vital that the anionic metal ion species adsorbed sufficiently onto the available oppositely charged sites of the micelles and that the micelles were retained efficiently by the membrane. Results obtained during the investigation made it possible to make certain predictions about the micellisation process. It was also found that, it was not only the metal ion: surfactant (M:S) ratio that was critical, but the presence of other electrolytes in the aqueous stream proved to have a huge impact on the capability of the MEUF system. Findings of this research study showed that the MEUF system using cetylpyridinium chloride (CPC) can be used to recover or retain Pt (lV) and Pd (ll) anions from industrial waste effluents. It was also found that PtCl6 2-, due to its greater adsorption capabilities onto the micelle surface than PdCl4 2- or PdCl3(H2O)-, was preferentially retained in neutral medium. This may be exploited as a possible means of separating the two metal ions. The developed system offers the following advantages over some traditional and current methods: simplified unit operation line flow process, smaller amounts of chemical usage and no solid toxic sludge to be disposed of. Applications of this work could be of vital importance in catalytic converter recycling, especially in Port Elizabeth where extensive automobile parts manufacturing occurs.
- Full Text:
- Date Issued: 2007
- Authors: Gwicana, Sakumzi
- Date: 2007
- Subjects: Micelles , Ultrafiltration , Palladium catalysts
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10414 , http://hdl.handle.net/10948/518 , Micelles , Ultrafiltration , Palladium catalysts
- Description: The project was concerned with studying the capability of a micellar-enhanced ultrafiltration system (MEUF) to remove platinum group metal ions namely Pt (lV) and Pd (ll) chloro anions from aqueous industrial waste effluents. South Africa has the world’s largest reserves of platinum group metals (PGMs) and other valuable metals such as manganese, chrome ores, titanium minerals etc. which are required for new automotive and other technologies, including fuel cells, catalytic converters and lighter components. The consistent loss with the industrial waste stream and the toxicological effects of these precious metals led to the need to develop new and effective methods to recover them from industrial waste effluents. With such a wide variety of fields where these PGMs are used and the failure of the traditional techniques namely sedimentation, fermentation etc. to effectively reduce or recover these highly toxic and precious metal ions prior to discharging industrial waste effluents, it is necessary to explore other techniques such as membrane technology that can be used to recover these valuable species from industrial waste streams. The present study involved the use of a cationic surfactant, viz cetylpyridinium chloride, which was introduced into an aqueous solution containing palladium and platinum metal anions. The surfactant forms charged micelles above a certain critical concentration value. The metal anions adsorb onto the available oppositely charged sites on the micelle surfaces and are then able to be retained by a suitable membrane. Hollow fibre ultrafiltration membranes with the MWCO of +/- 10 kD and +/-30nm pore size were used as a filter component in this study. For this MEUF system to be effective, it was vital that the anionic metal ion species adsorbed sufficiently onto the available oppositely charged sites of the micelles and that the micelles were retained efficiently by the membrane. Results obtained during the investigation made it possible to make certain predictions about the micellisation process. It was also found that, it was not only the metal ion: surfactant (M:S) ratio that was critical, but the presence of other electrolytes in the aqueous stream proved to have a huge impact on the capability of the MEUF system. Findings of this research study showed that the MEUF system using cetylpyridinium chloride (CPC) can be used to recover or retain Pt (lV) and Pd (ll) anions from industrial waste effluents. It was also found that PtCl6 2-, due to its greater adsorption capabilities onto the micelle surface than PdCl4 2- or PdCl3(H2O)-, was preferentially retained in neutral medium. This may be exploited as a possible means of separating the two metal ions. The developed system offers the following advantages over some traditional and current methods: simplified unit operation line flow process, smaller amounts of chemical usage and no solid toxic sludge to be disposed of. Applications of this work could be of vital importance in catalytic converter recycling, especially in Port Elizabeth where extensive automobile parts manufacturing occurs.
- Full Text:
- Date Issued: 2007
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