Determination of nonlinear optical properties of phthalocyanine regioisomers using computational models
- Date: 2020
- Subjects: Electrochemistry , Phthalocyanines , Nanoparticles , Nonlinear optics , Nonlinear optical spectroscopy , Refraction
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/166197 , vital:41337
- Description: This work investigates the effects of the nonlinear optical properties of four different constitutional isomers (C4h, C2v, Cs, and D2h) of a series of tetrasubstituted phthalocyanines (free-base 3-4-tert-butylphenoxyether phthalocyanines, free-base 4-4-tertbutylphenoxyether phthalocyanines, SnCl2 tetra substituted 3-4-tert-butylphenoxyether phthalocyanine, and SnCl2 tetra substituted 4-4-tert-butylphenoxyether phthalocyanine). The properties investigated were the real and imaginary components of the 3rd order hyperpolarizability, as well as the excited state absorption and refraction cross sections. The investigations were performed with a z-scan over a range of laser beam intensities. This work determined the imaginary component of the 3rd order hyperpolarizability for the free-base and SnCl2 3-4-tert-butylphenoxyether phthalocyanines and 4-4-tert-butylphenoxyether phthalocyanines to be highly dependent on the excited state cross sections. The refraction caused due to the real component of the 3rd order hyperpolarizability of the phthalocyanines was also investigated, however, the values found were strongly dependent on the laser beam intensity and the cause of this was investigated. A Five-level model was developed and run on GPGPU computing devices in order to isolate the absorption and refractive cross sections. Theeffects of the regio substitution on the excited state cross sections were also investigated, and the 1st singlet excited state and 1st triplet state absorption cross sections were calculated for all constitutional isomers. It was found that the symmetry of the constitutional isomers have a disproportionately large effect on the excited state absorption when compared to the ground state absorption. The nonlinear refractive properties of all constitutional isomers were also investigated, and the values of the parametric susceptibility are reported herein. The nonlinear refraction was found to have less effect than was seen in the nonlinear absorption. The 1st singlet excited state and 1st triplet state refractive cross sections of all constitutional isomer was determined. The results indicated that if more than one excited state was present and contributing to the nonlinear refraction, then more data than was collected here would be required. However, the 1st singlet excited state cross section were successfully determined for the free-base constitutional isomers. This work concluded that the region substitution affected the excited states more than the ground state.
- Full Text:
- Date: 2020
- Subjects: Electrochemistry , Phthalocyanines , Nanoparticles , Nonlinear optics , Nonlinear optical spectroscopy , Refraction
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/166197 , vital:41337
- Description: This work investigates the effects of the nonlinear optical properties of four different constitutional isomers (C4h, C2v, Cs, and D2h) of a series of tetrasubstituted phthalocyanines (free-base 3-4-tert-butylphenoxyether phthalocyanines, free-base 4-4-tertbutylphenoxyether phthalocyanines, SnCl2 tetra substituted 3-4-tert-butylphenoxyether phthalocyanine, and SnCl2 tetra substituted 4-4-tert-butylphenoxyether phthalocyanine). The properties investigated were the real and imaginary components of the 3rd order hyperpolarizability, as well as the excited state absorption and refraction cross sections. The investigations were performed with a z-scan over a range of laser beam intensities. This work determined the imaginary component of the 3rd order hyperpolarizability for the free-base and SnCl2 3-4-tert-butylphenoxyether phthalocyanines and 4-4-tert-butylphenoxyether phthalocyanines to be highly dependent on the excited state cross sections. The refraction caused due to the real component of the 3rd order hyperpolarizability of the phthalocyanines was also investigated, however, the values found were strongly dependent on the laser beam intensity and the cause of this was investigated. A Five-level model was developed and run on GPGPU computing devices in order to isolate the absorption and refractive cross sections. Theeffects of the regio substitution on the excited state cross sections were also investigated, and the 1st singlet excited state and 1st triplet state absorption cross sections were calculated for all constitutional isomers. It was found that the symmetry of the constitutional isomers have a disproportionately large effect on the excited state absorption when compared to the ground state absorption. The nonlinear refractive properties of all constitutional isomers were also investigated, and the values of the parametric susceptibility are reported herein. The nonlinear refraction was found to have less effect than was seen in the nonlinear absorption. The 1st singlet excited state and 1st triplet state refractive cross sections of all constitutional isomer was determined. The results indicated that if more than one excited state was present and contributing to the nonlinear refraction, then more data than was collected here would be required. However, the 1st singlet excited state cross section were successfully determined for the free-base constitutional isomers. This work concluded that the region substitution affected the excited states more than the ground state.
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Development of graphene materials and phthalocyanines for application in dye-sensitized solar cells
- Authors: Chindeka, Francis
- Date: 2020
- Subjects: Dye-sensitized solar cells , Graphene , Phthalocyanines , Molecular orbitals , Impedance spectroscopy
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/166092 , vital:41328
- Description: Two sets of dye-sensitized solar cells (DSSCs) were fabricated. In the first set, dye-sensitized solar cells (DSSC) were fabricated by incorporating graphene materials as catalysts at the counter electrode. Platinum was also used as a catalyst for comparative purposes. Different phthalocyanines: hydroxyl indium tetracarboxyphenoxy phthalocyanine (1), chloro indium octacarboxy phthalocyanine (2) and dibenzoic acid silicon phthalocyanine (3) were used as dyes. Complex 3 gave the highest power conversion efficiency (η) of 3.19% when using nitrogen doped reduced graphene oxide nanosheets (NrGONS) as a catalyst at the counter electrode, and TiO2 containing rGONS at the anode. The value obtained is close to 3.8% obtained when using Pt catalyst instead of NrGONS at the cathode, thus confirming that NrGONS is a promising candidate to replace the more expensive Pt. The study also shows that placing rGONS on both the anode and cathode improves efficiency. In the second set, DSSCs were fabricated by using 2(3,5-biscarboxyphenoxy), 9(10), 16(17), 23(24)-tri(tertbutyl) phthalocyaninato Cu (4) and Zn (5) complexes as dyes on the ITO-TiO2 photoanodes containing reduced graphene oxide nanosheets (rGONS) or nitrogen-doped rGONS (NrGONS). The evaluation of the assembled DSSCs revealed that using ITO-TiO2-NrGONS-CuPc (4) photoanode had the highest fill factor (FF) and power conversion efficiency (ɳ) of 69 % and 4.36 % respectively. These results show that the asymmetrical phthalocyanine complexes (4) and (5) showed significant improvement on the performance of the DSSC compared to previous work on symmetrical carboxylated phthalocyanines with ɳ = 3.19%.
- Full Text:
- Authors: Chindeka, Francis
- Date: 2020
- Subjects: Dye-sensitized solar cells , Graphene , Phthalocyanines , Molecular orbitals , Impedance spectroscopy
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/166092 , vital:41328
- Description: Two sets of dye-sensitized solar cells (DSSCs) were fabricated. In the first set, dye-sensitized solar cells (DSSC) were fabricated by incorporating graphene materials as catalysts at the counter electrode. Platinum was also used as a catalyst for comparative purposes. Different phthalocyanines: hydroxyl indium tetracarboxyphenoxy phthalocyanine (1), chloro indium octacarboxy phthalocyanine (2) and dibenzoic acid silicon phthalocyanine (3) were used as dyes. Complex 3 gave the highest power conversion efficiency (η) of 3.19% when using nitrogen doped reduced graphene oxide nanosheets (NrGONS) as a catalyst at the counter electrode, and TiO2 containing rGONS at the anode. The value obtained is close to 3.8% obtained when using Pt catalyst instead of NrGONS at the cathode, thus confirming that NrGONS is a promising candidate to replace the more expensive Pt. The study also shows that placing rGONS on both the anode and cathode improves efficiency. In the second set, DSSCs were fabricated by using 2(3,5-biscarboxyphenoxy), 9(10), 16(17), 23(24)-tri(tertbutyl) phthalocyaninato Cu (4) and Zn (5) complexes as dyes on the ITO-TiO2 photoanodes containing reduced graphene oxide nanosheets (rGONS) or nitrogen-doped rGONS (NrGONS). The evaluation of the assembled DSSCs revealed that using ITO-TiO2-NrGONS-CuPc (4) photoanode had the highest fill factor (FF) and power conversion efficiency (ɳ) of 69 % and 4.36 % respectively. These results show that the asymmetrical phthalocyanine complexes (4) and (5) showed significant improvement on the performance of the DSSC compared to previous work on symmetrical carboxylated phthalocyanines with ɳ = 3.19%.
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Effect of the nature of nanoparticles on the photophysicochemical properties and photodynamic antimicrobial chemotherapy of phthalocyanines
- Authors: Magadla, Aviwe
- Date: 2020
- Subjects: Nanoparticles , Phthalocyanines , Anti-infective agents -- Therapeutic use , Photochemotherapy , Photochemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/123107 , vital:35406
- Description: In this work, the syntheses and characterisation of Zn monocaffeic acid tri–tert–butyl phthalocyanine (1), Zn monocarboxyphenoxy tri– tert–butylphenoxyl phthalocyanine (2), tetrakis phenoxy N,N-dimethyl-4-(methylimino) phthalocyanine indium (III) chloride (3) and tetrakis N,N-dimethyl-4-(methylimino) phthalocyanine indium (III) chloride (5) are presented. Complexes 3 and 5 were further quartenised with 1,3- propanesultone to form corresponding complexes (4) and (6), respectively. Complexes 1 and 2 were covalently linked to amino functionalised nanoparticles (NPs). Complexes 3, 4, 5 and 6 where linked to oleic acid/oleylamine capped (OLA/OLM) silver-iron dimers (Ag-Fe3O4 OLA/OLM) and silver-iron core shell (Ag@Fe3O4 OLA/OLM) NPs via interaction between the nanoparticles and the imino group on the phthalocyanines. The phthalocyanine-NP conjugates afforded an increase in triplet quantum yields with a corresponding decrease in fluorescence quantum yield as compared to the phthalocyanine complexes alone. Complexes 3, 4 and their conjugates were then used for photodynamic antimicrobial chemotherapy on E. coli. The zwitterionic photosensitiser 4 and its conjugates showed better efficiency for photodynamic antimicrobial chemotherapy compared to their neutral counterparts.
- Full Text:
- Authors: Magadla, Aviwe
- Date: 2020
- Subjects: Nanoparticles , Phthalocyanines , Anti-infective agents -- Therapeutic use , Photochemotherapy , Photochemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/123107 , vital:35406
- Description: In this work, the syntheses and characterisation of Zn monocaffeic acid tri–tert–butyl phthalocyanine (1), Zn monocarboxyphenoxy tri– tert–butylphenoxyl phthalocyanine (2), tetrakis phenoxy N,N-dimethyl-4-(methylimino) phthalocyanine indium (III) chloride (3) and tetrakis N,N-dimethyl-4-(methylimino) phthalocyanine indium (III) chloride (5) are presented. Complexes 3 and 5 were further quartenised with 1,3- propanesultone to form corresponding complexes (4) and (6), respectively. Complexes 1 and 2 were covalently linked to amino functionalised nanoparticles (NPs). Complexes 3, 4, 5 and 6 where linked to oleic acid/oleylamine capped (OLA/OLM) silver-iron dimers (Ag-Fe3O4 OLA/OLM) and silver-iron core shell (Ag@Fe3O4 OLA/OLM) NPs via interaction between the nanoparticles and the imino group on the phthalocyanines. The phthalocyanine-NP conjugates afforded an increase in triplet quantum yields with a corresponding decrease in fluorescence quantum yield as compared to the phthalocyanine complexes alone. Complexes 3, 4 and their conjugates were then used for photodynamic antimicrobial chemotherapy on E. coli. The zwitterionic photosensitiser 4 and its conjugates showed better efficiency for photodynamic antimicrobial chemotherapy compared to their neutral counterparts.
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Metallophthalocyanines linked to metal nanoparticles and folic acid for use in photodynamic therapy of cancer and photoinactivation of bacterial microorganisms.
- Authors: Matlou, Gauta Gold
- Date: 2020
- Subjects: Cancer -- Photochemotherapy , Nanoparticles , Phthalocyanines , Anti-infective agents -- Therapeutic use , Photochemotherapy , Photochemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/166540 , vital:41377
- Description: This thesis presents on the synthesis and characterization of novel asymmetric and symmetrical metallophthalocyanines (MPcs) substituted with carboxylic acid functional groups and centrally metallated with zinc and indium. The MPcs are further covalently linked to cysteine capped silver nanoparticles (cys-AgNPs), amino functionalized magnetic nanoparticles (AMNPs) and folic acid (FA) through an amide bond between the carboxylic group of MPcs and the amino group of FA, cys-AgNPs or AMNPs. The covalent linkage of MPcs to FA improved the water solubility of MPcs and allowed for singlet oxygen quantum yield determination in water. Asymmetric MPcs and their conjugates were found to have improved photochemical and photophysical properties compared to symmetrical MPcs and their conjugates. The heavy atom effect of AMNPs and AgNPs improved the triplet and singlet oxygen quantum yields of MPcs. MPcs and their conjugates (MPc-FA, MPc-AMNPs, MPc-AgNPs) were found to have lower in vitro dark cytotoxicity and higher photodynamic therapy (PDT) activity on MCF-7 breast cancer cells. The water soluble MPc-FA had better PDT activity when compared to MPc-AMNPs due to the active targeting of folic acid-folate binding on cancer cell surface. MPcs and MPc-AgNPs conjugates also showed excellent in vitro cytotoxicity on S. aureus under light irradiation compared to dark cytotoxicity. The photosensitizing properties of MPcs and their conjugates are demonstrated for the first time in this thesis, both on breast cancer cells (MCF-7) through photodynamic therapy and on microorganisms (S. aureus) through photodynamic antimicrobial chemotherapy.
- Full Text:
- Authors: Matlou, Gauta Gold
- Date: 2020
- Subjects: Cancer -- Photochemotherapy , Nanoparticles , Phthalocyanines , Anti-infective agents -- Therapeutic use , Photochemotherapy , Photochemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/166540 , vital:41377
- Description: This thesis presents on the synthesis and characterization of novel asymmetric and symmetrical metallophthalocyanines (MPcs) substituted with carboxylic acid functional groups and centrally metallated with zinc and indium. The MPcs are further covalently linked to cysteine capped silver nanoparticles (cys-AgNPs), amino functionalized magnetic nanoparticles (AMNPs) and folic acid (FA) through an amide bond between the carboxylic group of MPcs and the amino group of FA, cys-AgNPs or AMNPs. The covalent linkage of MPcs to FA improved the water solubility of MPcs and allowed for singlet oxygen quantum yield determination in water. Asymmetric MPcs and their conjugates were found to have improved photochemical and photophysical properties compared to symmetrical MPcs and their conjugates. The heavy atom effect of AMNPs and AgNPs improved the triplet and singlet oxygen quantum yields of MPcs. MPcs and their conjugates (MPc-FA, MPc-AMNPs, MPc-AgNPs) were found to have lower in vitro dark cytotoxicity and higher photodynamic therapy (PDT) activity on MCF-7 breast cancer cells. The water soluble MPc-FA had better PDT activity when compared to MPc-AMNPs due to the active targeting of folic acid-folate binding on cancer cell surface. MPcs and MPc-AgNPs conjugates also showed excellent in vitro cytotoxicity on S. aureus under light irradiation compared to dark cytotoxicity. The photosensitizing properties of MPcs and their conjugates are demonstrated for the first time in this thesis, both on breast cancer cells (MCF-7) through photodynamic therapy and on microorganisms (S. aureus) through photodynamic antimicrobial chemotherapy.
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Photocatalysis of 4-chloro and 4-nonylphenols using novel symmetric phthalocyanines and asymmetric porphyrin supported on polyacrylonitrite nanofibres
- Authors: Jones, Benjamin Martin
- Date: 2020
- Subjects: Nanoparticles , Phthalocyanines , Electrospinning , Porphyrins , Nanofibers , Photocatalysis , Photocatalysis -- Environmental aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164770 , vital:41163
- Description: This work explores the synthesis and characterisation of novel symmetrical phthalocyanines and novel asymmetric porphyrins that have been embedded or linked respectively,and electrospun into fibres for application in the photocatalysis of environmental pollutants. The phthalocyanines contain pyrrole moieties without hetero atom linkers to maintain a rigid structure. The porphyrin contains a carboxy moiety utilized to construct an amide bond between the complex and the polymer prior to the spinning process. The new compounds were characterized by elemental analyses, proton nuclear magnetic resonance (HNMR)Fourier-transform infrared spectroscopy (FTIR), MALDI-TOF and UV-vis spectroscopy. The general trends of fluorescence, triplet and singlet oxygen quantum yields are described as well as their appropriate lifetimes. The photocatalytic activity of phthalocyanine embedded fibres were compared against those that had been dyed. Unfortunately, during the degradation process, the dyed fibres leeched compound and the studies could not be continued. It was seen that the porphyrin fibres linked to the polymer showed the most efficient photocatalytic activity against 4-cholorphenol and 4-nonylphenol due to irradiation at lower wavelengths consequently having higher frequencies and transferring more energy.
- Full Text:
- Authors: Jones, Benjamin Martin
- Date: 2020
- Subjects: Nanoparticles , Phthalocyanines , Electrospinning , Porphyrins , Nanofibers , Photocatalysis , Photocatalysis -- Environmental aspects
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164770 , vital:41163
- Description: This work explores the synthesis and characterisation of novel symmetrical phthalocyanines and novel asymmetric porphyrins that have been embedded or linked respectively,and electrospun into fibres for application in the photocatalysis of environmental pollutants. The phthalocyanines contain pyrrole moieties without hetero atom linkers to maintain a rigid structure. The porphyrin contains a carboxy moiety utilized to construct an amide bond between the complex and the polymer prior to the spinning process. The new compounds were characterized by elemental analyses, proton nuclear magnetic resonance (HNMR)Fourier-transform infrared spectroscopy (FTIR), MALDI-TOF and UV-vis spectroscopy. The general trends of fluorescence, triplet and singlet oxygen quantum yields are described as well as their appropriate lifetimes. The photocatalytic activity of phthalocyanine embedded fibres were compared against those that had been dyed. Unfortunately, during the degradation process, the dyed fibres leeched compound and the studies could not be continued. It was seen that the porphyrin fibres linked to the polymer showed the most efficient photocatalytic activity against 4-cholorphenol and 4-nonylphenol due to irradiation at lower wavelengths consequently having higher frequencies and transferring more energy.
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Symmetry and asymmetry in electrocatalysis: enhancing the electrocatalytic activity of phthalocyanines through synergy with doped graphene quantum dots
- Nkhahle, Reitumetse Precious
- Authors: Nkhahle, Reitumetse Precious
- Date: 2020
- Subjects: Phthalocyanines , Quantum dots , Graphene
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/117585 , vital:34529
- Description: An exploration on the enhancement of the electrocatalytic activity of phthalocyanines (Pcs) through coupling with a series of graphene quantum dots (GQDs) is undertaken. The preliminary studies using symmetrical Pcs, a cobalt and an iron chloride tetra substituted diethylaminophenoxy Pc (complexes 1 and 2), for the electro-oxidation of nitrite revealed through the various sequential modifications that doped GQDs fare better than their pristine counterparts with respect to improving the electrocatalytic behaviour of Pcs, in particular, the nitrogen-doped GQDs (NGQDs). Following up on this, a series of asymmetric Pc complexes; 2,9,16-tris-(4-tert-butylphenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (3), 2,9,16-tris-(4-tert-butylphenoxy) mono aminophenoxy phthalocyanato cobalt (II) (4), 2,9,16-tris-(3-diethylamino)phenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (5) and 2,9,16-tris-(3-diethylamino)phenoxy) mono aminophenoxy phthalocyanato cobalt (II) (6) was prepared in which push-pull systems were compared to other asymmetric complexes that lack this effect towards the electrocatalytic sensing of hydrazine. All asymmetric complexes (3-6) were π-stacked to the NGQDs while those with an NH2 group (4 and 6), were also covalently linked to the NGQDs. These complexes and their corresponding conjugates were characterized accordingly and applied as electrocatalysts in the oxidation of hydrazine. The electrochemical studies revealed that π π stacking yields better responses (higher sensitivities and lower limits of detection) than covalent linking because there are less forces acting on the graphene network. Covalent linking introduces both tensile and compressive forces which in turn results in an increase in the ID/IG ratio and that is unfavourable for electrocatalysis. In comparing the electrodes composed of the π-stacked conjugates to those altered through sequential modifications, despite the conditions not being the same, it can be inferred that the magnitude of the electrostatic forces between the Pcs and the GQDs also plays a significant role in electrocatalysis. The π-stacked conjugates, owing to the manner in which they were prepared, have stronger electrostatic forces acting between the Pc and GQDs hence they were able to elicit a better electrochemical response than the sequentially modified electrodes. In addition to that, it appears that asymmetric Pcs are better electrocatalysts in comparison to the symmetric Pcs.
- Full Text:
- Authors: Nkhahle, Reitumetse Precious
- Date: 2020
- Subjects: Phthalocyanines , Quantum dots , Graphene
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/117585 , vital:34529
- Description: An exploration on the enhancement of the electrocatalytic activity of phthalocyanines (Pcs) through coupling with a series of graphene quantum dots (GQDs) is undertaken. The preliminary studies using symmetrical Pcs, a cobalt and an iron chloride tetra substituted diethylaminophenoxy Pc (complexes 1 and 2), for the electro-oxidation of nitrite revealed through the various sequential modifications that doped GQDs fare better than their pristine counterparts with respect to improving the electrocatalytic behaviour of Pcs, in particular, the nitrogen-doped GQDs (NGQDs). Following up on this, a series of asymmetric Pc complexes; 2,9,16-tris-(4-tert-butylphenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (3), 2,9,16-tris-(4-tert-butylphenoxy) mono aminophenoxy phthalocyanato cobalt (II) (4), 2,9,16-tris-(3-diethylamino)phenoxy) mono carboxyphenoxy phthalocyanato cobalt (II) (5) and 2,9,16-tris-(3-diethylamino)phenoxy) mono aminophenoxy phthalocyanato cobalt (II) (6) was prepared in which push-pull systems were compared to other asymmetric complexes that lack this effect towards the electrocatalytic sensing of hydrazine. All asymmetric complexes (3-6) were π-stacked to the NGQDs while those with an NH2 group (4 and 6), were also covalently linked to the NGQDs. These complexes and their corresponding conjugates were characterized accordingly and applied as electrocatalysts in the oxidation of hydrazine. The electrochemical studies revealed that π π stacking yields better responses (higher sensitivities and lower limits of detection) than covalent linking because there are less forces acting on the graphene network. Covalent linking introduces both tensile and compressive forces which in turn results in an increase in the ID/IG ratio and that is unfavourable for electrocatalysis. In comparing the electrodes composed of the π-stacked conjugates to those altered through sequential modifications, despite the conditions not being the same, it can be inferred that the magnitude of the electrostatic forces between the Pcs and the GQDs also plays a significant role in electrocatalysis. The π-stacked conjugates, owing to the manner in which they were prepared, have stronger electrostatic forces acting between the Pc and GQDs hence they were able to elicit a better electrochemical response than the sequentially modified electrodes. In addition to that, it appears that asymmetric Pcs are better electrocatalysts in comparison to the symmetric Pcs.
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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.
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- 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.
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