Metallophthalocyanine-gold nanoparticle conjugates for photodynamic antimicrobial chemotherapy
- Mthethwa, Thandekile Phakamisiwe
- Authors: Mthethwa, Thandekile Phakamisiwe
- Date: 2015
- Subjects: Nanochemistry , Phthalocyanines , Photochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4543 , http://hdl.handle.net/10962/d1017923
- Description: This thesis presents the synthesis of neutral and cationic metallophthalocyanines and their gold nanoparticles conjugates. The spectroscopic characterization of these compounds is presented herein. The studies presented in this work shows that the conjugation of gold nanoparticles influenced both photophysical and photochemical properties. Gold nanoparticles were found to enhance the singlet oxygen quantum yield while lowering the fluorescence quantum yields. This work also looks at the effect of anisotropic gold nanoparticles such as nanorods and bipyramids on the photophysical behaviour of the metallophthalocyanines. The effect of the size of the gold nanorods was investigated herein. The results show that photophysical and photochemical properties can be influenced by both size and shape of the nanoparticles. Physical characterization about the loading of nanoparticles was also looked into. Parameters such as the surface area, the number of surface atoms, the number of atoms as well as the number of nanoparticles loaded on the surface of the phthalocyanines were studied. The self-assembled monolayers formed by phthalocyanines on gold surfaces were studied using the X-ray photoelectron spectroscopy (XPS). The gold nanoparticles synthesized herein include both organic and water soluble, different capping agents (citrate, tetraammonium bromide (TAOBr) and cetrimethylammonium bromide (CTAB). The concentration of the gold nanoparticles was measured on the inductively coupled plasma (ICP) and their size and shape were obtained from the transmission electron microscopy (TEM) images. A cationic aluminium phthalocyanine and its conjugates were used for photoinactivation of bacteria and fungi. The results show significant reduction and higher activity in the presence of gold nanoparticles, especially nanorods. A small chapter in this work presents an attempted work on the binding of metallothionein protein with protophorphyrin (IX). The pH and concentration dependent binding studies were investigated
- Full Text:
- Date Issued: 2015
- Authors: Mthethwa, Thandekile Phakamisiwe
- Date: 2015
- Subjects: Nanochemistry , Phthalocyanines , Photochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4543 , http://hdl.handle.net/10962/d1017923
- Description: This thesis presents the synthesis of neutral and cationic metallophthalocyanines and their gold nanoparticles conjugates. The spectroscopic characterization of these compounds is presented herein. The studies presented in this work shows that the conjugation of gold nanoparticles influenced both photophysical and photochemical properties. Gold nanoparticles were found to enhance the singlet oxygen quantum yield while lowering the fluorescence quantum yields. This work also looks at the effect of anisotropic gold nanoparticles such as nanorods and bipyramids on the photophysical behaviour of the metallophthalocyanines. The effect of the size of the gold nanorods was investigated herein. The results show that photophysical and photochemical properties can be influenced by both size and shape of the nanoparticles. Physical characterization about the loading of nanoparticles was also looked into. Parameters such as the surface area, the number of surface atoms, the number of atoms as well as the number of nanoparticles loaded on the surface of the phthalocyanines were studied. The self-assembled monolayers formed by phthalocyanines on gold surfaces were studied using the X-ray photoelectron spectroscopy (XPS). The gold nanoparticles synthesized herein include both organic and water soluble, different capping agents (citrate, tetraammonium bromide (TAOBr) and cetrimethylammonium bromide (CTAB). The concentration of the gold nanoparticles was measured on the inductively coupled plasma (ICP) and their size and shape were obtained from the transmission electron microscopy (TEM) images. A cationic aluminium phthalocyanine and its conjugates were used for photoinactivation of bacteria and fungi. The results show significant reduction and higher activity in the presence of gold nanoparticles, especially nanorods. A small chapter in this work presents an attempted work on the binding of metallothionein protein with protophorphyrin (IX). The pH and concentration dependent binding studies were investigated
- Full Text:
- Date Issued: 2015
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:
- Date Issued: 2020
- 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:
- Date Issued: 2020
Removal and photocatalysis of 4-Nitrophenol using metallophthalocyanines
- Authors: Marais, Eloise Ann
- Date: 2008
- Subjects: Photocatalysis , Catalysis , Electrochemistry , Nitrophenols , Phthalocyanines
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4343 , http://hdl.handle.net/10962/d1005005 , Photocatalysis , Catalysis , Electrochemistry , Nitrophenols , Phthalocyanines
- Description: Photodegradation of 4-nitrophenol (4-Np) in the presence of water-soluble zinc phthalocyanines and water-insoluble metallophthalocyanines is reported. The water-soluble phthalocyanines employed include zinc tetrasulphophthalocyanine (ZnPcS[subscript 4]), zinc octacarboxyphthalocyanine (ZnPc(COOH)[subscript 8]) and a sulphonated ZnPc containing a mixture of differently sulphonated derivatives (ZnPcS[subscript mix]), while the water-insoluble phthalocyanines used include unsubstituted magnesium (MgPc), zinc (ZnPc) and chloroaluminium (ClAlPc) phthalocyanine complexes and the ring-substituted zinc tetranitro (ZnPc(NO[subscript 2])[subscript 4]), zinc tetraamino (ZnPc(NH[subscript 2])[subscript 4]), zinc hexadecafluoro (ZnPcF[subscript 16]) and zinc hexadecachloro (ZnPcCl[subscript 16]) phthalocyanines. The most effective water-soluble photocatalyst is ZnPcS[subscript mix] in terms of the high quantum yield obtained for 4-Np degradation (Φ[subscript 4-Np]) as well as its photostability. While ZnPc(COOH)[subscript 8] has the highest Φ[subscript 4-Np] value relative to the other water-soluble complexes, it degrades readily during photocatalysis. The Φ[subscript 4-Np] values were closely related to the singlet oxygen quantum yields Φ[subscript Δ] and hence aggregation. The rate constants for the reaction with 4-Np were kr = 0.67 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPcS[subscript mix] and 7.7 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPc(COOH)[subscript 8]. ClAlPc is the most effective photocatalyst relative to the other heterogeneous photocatalysts for the phototransformation of 4-Np, with 89 ± 8.4 % degradation of 4-Np achieved after 100 min. The least effective catalysts were ZnPcCl[subscript 16] and MgPc. The final products of the photocatalysis of 4-Np in the presence of the homogeneous photocatalysts include 4-nitrocatechol and hydroquinone, while degradation of 4-Np in the presence of the heterogeneous photocatalysts resulted in fumaric acid and 4-nitrocatechol. ClAlPc was employed for the heterogeneous photocatalysis of the non-systemic insecticide, methyl paraoxon. Complete degradation of the pesticide was confirmed by the disappearance of the HPLC trace for methyl paraoxon after 100 min of irradiation with visible light. The removal of 4-Np from an aqueous medium using commercially available Amberlite[superscript ®] IRA-900 modified with metal phthalocyanines was also investigated. The metallophthalocyanines immobilised onto the surface of Amberlite[superscript ®] IRA-900 include Fe (FePcS[subscript 4]), Co (CoPcS[subscript 4]) and Ni (NiPcS[subscript 4]) tetrasulphophthalocyanines, and differently sulphonated phthalocyanine mixtures of Fe (FePcS[subscript mix]), Co (CoPcS[subscript mix]) and Ni (NiPcS[subscript mix]). Adsorption rates were fastest for the modified adsorbents at pH 9. Using the Langmuir-Hinshelwood kinetic model, the complexes showed the following order of 4-Np adsorption: CoPcS[subscript mix] > NiPcS[subscript 4] > NiPcS[subscript mix] > FePcS[subscript 4] > FePcS[subscript mix] > CoPcS[subscript 4]. The adsorbents were regenerated using dilute HNO[subscript 3], with 76 % (7.6 x 10[superscript -5] mol) of 4-Np recovered within 150 min.
- Full Text:
- Date Issued: 2008
- Authors: Marais, Eloise Ann
- Date: 2008
- Subjects: Photocatalysis , Catalysis , Electrochemistry , Nitrophenols , Phthalocyanines
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4343 , http://hdl.handle.net/10962/d1005005 , Photocatalysis , Catalysis , Electrochemistry , Nitrophenols , Phthalocyanines
- Description: Photodegradation of 4-nitrophenol (4-Np) in the presence of water-soluble zinc phthalocyanines and water-insoluble metallophthalocyanines is reported. The water-soluble phthalocyanines employed include zinc tetrasulphophthalocyanine (ZnPcS[subscript 4]), zinc octacarboxyphthalocyanine (ZnPc(COOH)[subscript 8]) and a sulphonated ZnPc containing a mixture of differently sulphonated derivatives (ZnPcS[subscript mix]), while the water-insoluble phthalocyanines used include unsubstituted magnesium (MgPc), zinc (ZnPc) and chloroaluminium (ClAlPc) phthalocyanine complexes and the ring-substituted zinc tetranitro (ZnPc(NO[subscript 2])[subscript 4]), zinc tetraamino (ZnPc(NH[subscript 2])[subscript 4]), zinc hexadecafluoro (ZnPcF[subscript 16]) and zinc hexadecachloro (ZnPcCl[subscript 16]) phthalocyanines. The most effective water-soluble photocatalyst is ZnPcS[subscript mix] in terms of the high quantum yield obtained for 4-Np degradation (Φ[subscript 4-Np]) as well as its photostability. While ZnPc(COOH)[subscript 8] has the highest Φ[subscript 4-Np] value relative to the other water-soluble complexes, it degrades readily during photocatalysis. The Φ[subscript 4-Np] values were closely related to the singlet oxygen quantum yields Φ[subscript Δ] and hence aggregation. The rate constants for the reaction with 4-Np were kr = 0.67 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPcS[subscript mix] and 7.7 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPc(COOH)[subscript 8]. ClAlPc is the most effective photocatalyst relative to the other heterogeneous photocatalysts for the phototransformation of 4-Np, with 89 ± 8.4 % degradation of 4-Np achieved after 100 min. The least effective catalysts were ZnPcCl[subscript 16] and MgPc. The final products of the photocatalysis of 4-Np in the presence of the homogeneous photocatalysts include 4-nitrocatechol and hydroquinone, while degradation of 4-Np in the presence of the heterogeneous photocatalysts resulted in fumaric acid and 4-nitrocatechol. ClAlPc was employed for the heterogeneous photocatalysis of the non-systemic insecticide, methyl paraoxon. Complete degradation of the pesticide was confirmed by the disappearance of the HPLC trace for methyl paraoxon after 100 min of irradiation with visible light. The removal of 4-Np from an aqueous medium using commercially available Amberlite[superscript ®] IRA-900 modified with metal phthalocyanines was also investigated. The metallophthalocyanines immobilised onto the surface of Amberlite[superscript ®] IRA-900 include Fe (FePcS[subscript 4]), Co (CoPcS[subscript 4]) and Ni (NiPcS[subscript 4]) tetrasulphophthalocyanines, and differently sulphonated phthalocyanine mixtures of Fe (FePcS[subscript mix]), Co (CoPcS[subscript mix]) and Ni (NiPcS[subscript mix]). Adsorption rates were fastest for the modified adsorbents at pH 9. Using the Langmuir-Hinshelwood kinetic model, the complexes showed the following order of 4-Np adsorption: CoPcS[subscript mix] > NiPcS[subscript 4] > NiPcS[subscript mix] > FePcS[subscript 4] > FePcS[subscript mix] > CoPcS[subscript 4]. The adsorbents were regenerated using dilute HNO[subscript 3], with 76 % (7.6 x 10[superscript -5] mol) of 4-Np recovered within 150 min.
- Full Text:
- Date Issued: 2008
The systematic assembly of prostate specific antigen electrochemical sensors based on asymmetric Co(II) phthalocyanines, graphitic quantum dots and an aptamer
- Authors: Nxele, Siphesihle Robin
- Date: 2022-04-08
- Subjects: Prostate-specific antigen , Electrochemical sensors , Phthalocyanines , Quantum dots , Co(II) phthalocyanines , Aptamer
- Language: English
- Type: Doctoral thesis , text
- Identifier: http://hdl.handle.net/10962/232893 , vital:50035 , DOI 10.21504/10962/232893
- Description: The need for low-cost, efficient and simple diagnostic tools has led to more research going into this subject, with the aim of making such medical devices more accessible where they are needed. This has led to more researchers developing point-of-care devices for this purpose worldwide, by sensor fabrication. This thesis focuses on electrochemical sensor development for the early diagnosis of prostate cancer. It is common knowledge that prostate cancer is one of the most prevalent carcinomas that have claimed lives due to late diagnosis where even the most invasive treatments have failed. For this reason, development of early detection devices that can even be used in the comfort of home is necessary and quite crucial. Electrochemical sensors have gained much attention due to their ease of fabrication, cost effectiveness, simplicity, ease of use and high efficiency. Using nanocomposites as modifiers has also become popular as they provide greater stability and improve detection limits when used together with biomolecules. With that said, the work reported herein has combined nanocomposites of graphenebased quantum dots, gold nanoparticles, phthalocyanines and an aptamer in order to fabricate aptasensors for the electrochemical detection of prostate cancer biomarker. The aptamer is specifically designed to bind to the biomarker, and the nanocomposites are expected to enhance current output thus lowering detection limits and increasing stability and efficiency. Reproducible results are also expected. Prior to the detection of the prostate cancer biomarker, the quantum dots-phthalocyanine nanohybrids were used to detect L-cysteine, which is an amino acid, in order to verify the synergistic effects as electrode modifiers that lead to the enhancement of current output. This increase in current output is then v exploited for the improvement of aptasensor functionality upon incorporation of the aptamer, for the detection of prostate specific antigen. The research in this thesis has been carried out with the intention of contributing to the world of medical research, more so because of the ever-increasing need for medical care to become accessible to all and not only to those who can afford expensive technologies and treatments. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-04-08
- Authors: Nxele, Siphesihle Robin
- Date: 2022-04-08
- Subjects: Prostate-specific antigen , Electrochemical sensors , Phthalocyanines , Quantum dots , Co(II) phthalocyanines , Aptamer
- Language: English
- Type: Doctoral thesis , text
- Identifier: http://hdl.handle.net/10962/232893 , vital:50035 , DOI 10.21504/10962/232893
- Description: The need for low-cost, efficient and simple diagnostic tools has led to more research going into this subject, with the aim of making such medical devices more accessible where they are needed. This has led to more researchers developing point-of-care devices for this purpose worldwide, by sensor fabrication. This thesis focuses on electrochemical sensor development for the early diagnosis of prostate cancer. It is common knowledge that prostate cancer is one of the most prevalent carcinomas that have claimed lives due to late diagnosis where even the most invasive treatments have failed. For this reason, development of early detection devices that can even be used in the comfort of home is necessary and quite crucial. Electrochemical sensors have gained much attention due to their ease of fabrication, cost effectiveness, simplicity, ease of use and high efficiency. Using nanocomposites as modifiers has also become popular as they provide greater stability and improve detection limits when used together with biomolecules. With that said, the work reported herein has combined nanocomposites of graphenebased quantum dots, gold nanoparticles, phthalocyanines and an aptamer in order to fabricate aptasensors for the electrochemical detection of prostate cancer biomarker. The aptamer is specifically designed to bind to the biomarker, and the nanocomposites are expected to enhance current output thus lowering detection limits and increasing stability and efficiency. Reproducible results are also expected. Prior to the detection of the prostate cancer biomarker, the quantum dots-phthalocyanine nanohybrids were used to detect L-cysteine, which is an amino acid, in order to verify the synergistic effects as electrode modifiers that lead to the enhancement of current output. This increase in current output is then v exploited for the improvement of aptasensor functionality upon incorporation of the aptamer, for the detection of prostate specific antigen. The research in this thesis has been carried out with the intention of contributing to the world of medical research, more so because of the ever-increasing need for medical care to become accessible to all and not only to those who can afford expensive technologies and treatments. , Thesis (PhD) -- Faculty of Science, Chemistry, 2022
- Full Text:
- Date Issued: 2022-04-08
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.
- Full Text:
- Date Issued: 2019
- 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.
- Full Text:
- Date Issued: 2019
Effects of Axial Ligands on the Photosensitising Properties of Silicon Octaphenoxyphthalocyanines
- Authors: Maree, Machiel David
- Date: 2002
- Subjects: Ligands , Photochemotherapy , Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4553 , http://hdl.handle.net/10962/d1018246
- Description: Various axially substituted Silicon octaphenoxyphthalocyanines were synthesised as potential photosensitisers in the photodynamic therapy of cancer. Conventional reflux reactions were used for synthesis as well as new microwave irradiation reactions, wherein the reaction times were decreased tenfold with a marginal increase in reaction yield and product purity. An interesting series of oligomeric (dimer to a nonamer) silicon octaphenoxyphthalocyanines were also successfully synthesised in a reaction similar to polymerisation reactions. These compounds were found to undergo an axial ligand transformation upon irradiation with red light (> 600 nm) in dimethylsulphoxide solution. All the ligands were transformed into the dihydroxy silicon octaphenoxyphthalocyanine with varying degrees of phototransformation quantum yields ranging in order from 10⁻³ to 10⁻⁵ depending on the axial ligand involved. During and after axial ligand transformations a photodegredation of the dihydroxy silicon octaphenoxy phthalocyanine was observed upon continued irradiation. The oligomers were found to undergo the same axial ligand transformation process with a phototransformation quantum yield of 10⁻⁵ The singlet oxygen quantum yields of the unaggregated monomeric silicon octaphenoxy phthalocyanines were all found to be approximately 0.2 with the exception of a compound with two (trihexyl)siloxy axial substituents that had a singlet oxygen quantum yield of approximately 0.4 in dimethylsulphoxide solutions. The oligomers showed a surprising trend of an increase in singlet oxygen quantum yield with an increase in phthalocyanine ring number up to the pentamer and then a dramatic decrease to the nonamer. The triplet quantum yield and triplet lifetime were determined by laser flash photolysis for selected compounds and no correlation was observed with any of these properties and the singlet oxygen quantum yields. These selected compounds all fluoresce and a very good correlation was found between the fluorescence lifetimes determined experimentally by laser photolysis and the Strickler-Berg equation for the non-aggregated compounds. Electrochemical measurements also indicate the importance of the axial ligands upon the behaviour of the phthalocyanines as cyclic voltammetric behaviour was determined by the nature of the axial ligand.
- Full Text:
- Date Issued: 2002
- Authors: Maree, Machiel David
- Date: 2002
- Subjects: Ligands , Photochemotherapy , Phthalocyanines
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4553 , http://hdl.handle.net/10962/d1018246
- Description: Various axially substituted Silicon octaphenoxyphthalocyanines were synthesised as potential photosensitisers in the photodynamic therapy of cancer. Conventional reflux reactions were used for synthesis as well as new microwave irradiation reactions, wherein the reaction times were decreased tenfold with a marginal increase in reaction yield and product purity. An interesting series of oligomeric (dimer to a nonamer) silicon octaphenoxyphthalocyanines were also successfully synthesised in a reaction similar to polymerisation reactions. These compounds were found to undergo an axial ligand transformation upon irradiation with red light (> 600 nm) in dimethylsulphoxide solution. All the ligands were transformed into the dihydroxy silicon octaphenoxyphthalocyanine with varying degrees of phototransformation quantum yields ranging in order from 10⁻³ to 10⁻⁵ depending on the axial ligand involved. During and after axial ligand transformations a photodegredation of the dihydroxy silicon octaphenoxy phthalocyanine was observed upon continued irradiation. The oligomers were found to undergo the same axial ligand transformation process with a phototransformation quantum yield of 10⁻⁵ The singlet oxygen quantum yields of the unaggregated monomeric silicon octaphenoxy phthalocyanines were all found to be approximately 0.2 with the exception of a compound with two (trihexyl)siloxy axial substituents that had a singlet oxygen quantum yield of approximately 0.4 in dimethylsulphoxide solutions. The oligomers showed a surprising trend of an increase in singlet oxygen quantum yield with an increase in phthalocyanine ring number up to the pentamer and then a dramatic decrease to the nonamer. The triplet quantum yield and triplet lifetime were determined by laser flash photolysis for selected compounds and no correlation was observed with any of these properties and the singlet oxygen quantum yields. These selected compounds all fluoresce and a very good correlation was found between the fluorescence lifetimes determined experimentally by laser photolysis and the Strickler-Berg equation for the non-aggregated compounds. Electrochemical measurements also indicate the importance of the axial ligands upon the behaviour of the phthalocyanines as cyclic voltammetric behaviour was determined by the nature of the axial ligand.
- Full Text:
- Date Issued: 2002
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.
- Full Text:
- Date Issued: 2019
- 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.
- Full Text:
- Date Issued: 2019
Characterization and application of phthalocyanine-gold nanoparticle conjugates
- Authors: Tombe, Sekai Lana
- Date: 2013
- Subjects: Phthalocyanines , Gold , Zinc , Nanoparticles , Bioconjugates , Photochemistry , Photocatalysis , Electrospinning , Polymers , Pollutants , Phenols , Azo dyes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4293 , http://hdl.handle.net/10962/d1004517 , Phthalocyanines , Gold , Zinc , Nanoparticles , Bioconjugates , Photochemistry , Photocatalysis , Electrospinning , Polymers , Pollutants , Phenols , Azo dyes
- Description: This work presents the syntheses, photophysical and photochemical characterization of arylthio zinc phthalocyanines and their gold nanoparticle conjugates. Spectroscopic and microscopic studies confirmed the formation of the phthalocyanine-gold nanoparticle conjugates which exhibited enhanced photophysicochemical properties in comparison to the phthalocyanines. The studies showed that the presence of gold nanoparticles significantly lowered fluorescence quantum yields and lifetimes. However, this interaction did not restrict the formation of excited singlet and triplet states and hence the formation of singlet oxygen required for photocatalysis. The conjugates showed significantly higher singlet oxygen quantum yields and therefore enhanced photocatalytic activity compared to the phthalocyanines. The zinc phthalocyanines and their gold nanoparticle conjugates were successfully incorporated into electrospun polymer fibers. Spectral characteristics of the functionalized electrospun fibers indicated that the phthalocyanines and phthalocyanine-gold nanoparticle conjugates were bound and their integrity was maintained within the polymeric fiber matrices. The photophysical and photochemical properties of the complexes were equally maintained within the electrospun fibers. The functionalized fibers were applied for the photoconversion of 4-chlorophenol and Orange G as model organic pollutants. , Microsoft� Word 2010 , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 2013
- Authors: Tombe, Sekai Lana
- Date: 2013
- Subjects: Phthalocyanines , Gold , Zinc , Nanoparticles , Bioconjugates , Photochemistry , Photocatalysis , Electrospinning , Polymers , Pollutants , Phenols , Azo dyes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4293 , http://hdl.handle.net/10962/d1004517 , Phthalocyanines , Gold , Zinc , Nanoparticles , Bioconjugates , Photochemistry , Photocatalysis , Electrospinning , Polymers , Pollutants , Phenols , Azo dyes
- Description: This work presents the syntheses, photophysical and photochemical characterization of arylthio zinc phthalocyanines and their gold nanoparticle conjugates. Spectroscopic and microscopic studies confirmed the formation of the phthalocyanine-gold nanoparticle conjugates which exhibited enhanced photophysicochemical properties in comparison to the phthalocyanines. The studies showed that the presence of gold nanoparticles significantly lowered fluorescence quantum yields and lifetimes. However, this interaction did not restrict the formation of excited singlet and triplet states and hence the formation of singlet oxygen required for photocatalysis. The conjugates showed significantly higher singlet oxygen quantum yields and therefore enhanced photocatalytic activity compared to the phthalocyanines. The zinc phthalocyanines and their gold nanoparticle conjugates were successfully incorporated into electrospun polymer fibers. Spectral characteristics of the functionalized electrospun fibers indicated that the phthalocyanines and phthalocyanine-gold nanoparticle conjugates were bound and their integrity was maintained within the polymeric fiber matrices. The photophysical and photochemical properties of the complexes were equally maintained within the electrospun fibers. The functionalized fibers were applied for the photoconversion of 4-chlorophenol and Orange G as model organic pollutants. , Microsoft� Word 2010 , Adobe Acrobat 9.53 Paper Capture Plug-in
- Full Text:
- Date Issued: 2013
Evaluation of metallophthalocyanine functionalized photocatalytic asymmetric polymer membranes for pollution control and antimicrobial activity
- Mafukidze, Donovan Musizvinoda Chidyamurimi
- Authors: Mafukidze, Donovan Musizvinoda Chidyamurimi
- Date: 2021
- Subjects: Photosensitizing compounds , Water -- Purification -- Photocatalysis , Phthalocyanines , Polymeric membranes , Porphyrins
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/171357 , vital:42052 , 10.21504/10962/171357
- Description: The conceptualisation of photosensitizing water treatment polymer membranes using phthalocyanine based photosensitizers is reported in this thesis. The key to successful preparation of stable photoactive polymer membranes was established as the covalent anchorage of the photosensitizer to a polymer, which was proven by singlet oxygen generation by the membranes without photosensitizer deterioration. Despite this limitation, the covalent linkage-incapable unsubstituted zinc (II) phthalocyanine (complex 2) was applied as a nanoconjugate of graphene quantum dots (2π(GQDs)). 2π(GQDs) was formed through π-π stacking, and was then covalently anchored, as a proof of concept. This concept was also applied to 2-(4-carboxyphenoxy) phthalocyaninato zinc (II) (complex 3) which is capable of covalent linkage but proved to deteriorate the efficiency of singlet oxygen formation with comparison to the covalent conjugates. Singlet oxygen generation by functionalized polymer membranes rendered them photocatalytic in the degradation of organic pollutants and microorganisms in water. Organic pollutant degradation capability was exemplified by 2π(GQDs) and a porphyrin-phthalocyanine heterodyad (complex 10) functionalized membranes (2π(GQDs)-memb and 10-memb respectively), where a MPc loading of approximately 0.139 μmol MPc/g of membrane was able to achieve a 4-chlorophenol degradation rate of 3.77 × 10−6 mol L−1 min−1 in a second order reaction with an initial 4-chlorophenol concentration of 3.24 × 10−4 mol L−1 for 2π(GQDs)-memb as an example. Antibacterial studies against S.aureus using a quaternized MPc and conjugates of silver triangular nanoprisms with zinc (II) and indium (III) MPcs showed note-worthy improvements in photodynamic antimicrobial chemotherapy (PACT) activity in comparison to the unquaternized MPc precursor, and the free zinc and indium MPcs respectively. Functionalization of polymer membranes with these higher activity photosensitizers translated to the formation of potentially superior biological fouling resistant membranes. The use of porphyrin-phthalocyanine polynuclei arrays (complex 10) in polymer membrane functionalization resulted in the use of a wider wavelength range (white light). The findings from this work as a whole, thus presents the potential applicability of phthalocyanine functionalized polymer membranes in water treatment technology.
- Full Text:
- Date Issued: 2021
- Authors: Mafukidze, Donovan Musizvinoda Chidyamurimi
- Date: 2021
- Subjects: Photosensitizing compounds , Water -- Purification -- Photocatalysis , Phthalocyanines , Polymeric membranes , Porphyrins
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/171357 , vital:42052 , 10.21504/10962/171357
- Description: The conceptualisation of photosensitizing water treatment polymer membranes using phthalocyanine based photosensitizers is reported in this thesis. The key to successful preparation of stable photoactive polymer membranes was established as the covalent anchorage of the photosensitizer to a polymer, which was proven by singlet oxygen generation by the membranes without photosensitizer deterioration. Despite this limitation, the covalent linkage-incapable unsubstituted zinc (II) phthalocyanine (complex 2) was applied as a nanoconjugate of graphene quantum dots (2π(GQDs)). 2π(GQDs) was formed through π-π stacking, and was then covalently anchored, as a proof of concept. This concept was also applied to 2-(4-carboxyphenoxy) phthalocyaninato zinc (II) (complex 3) which is capable of covalent linkage but proved to deteriorate the efficiency of singlet oxygen formation with comparison to the covalent conjugates. Singlet oxygen generation by functionalized polymer membranes rendered them photocatalytic in the degradation of organic pollutants and microorganisms in water. Organic pollutant degradation capability was exemplified by 2π(GQDs) and a porphyrin-phthalocyanine heterodyad (complex 10) functionalized membranes (2π(GQDs)-memb and 10-memb respectively), where a MPc loading of approximately 0.139 μmol MPc/g of membrane was able to achieve a 4-chlorophenol degradation rate of 3.77 × 10−6 mol L−1 min−1 in a second order reaction with an initial 4-chlorophenol concentration of 3.24 × 10−4 mol L−1 for 2π(GQDs)-memb as an example. Antibacterial studies against S.aureus using a quaternized MPc and conjugates of silver triangular nanoprisms with zinc (II) and indium (III) MPcs showed note-worthy improvements in photodynamic antimicrobial chemotherapy (PACT) activity in comparison to the unquaternized MPc precursor, and the free zinc and indium MPcs respectively. Functionalization of polymer membranes with these higher activity photosensitizers translated to the formation of potentially superior biological fouling resistant membranes. The use of porphyrin-phthalocyanine polynuclei arrays (complex 10) in polymer membrane functionalization resulted in the use of a wider wavelength range (white light). The findings from this work as a whole, thus presents the potential applicability of phthalocyanine functionalized polymer membranes in water treatment technology.
- Full Text:
- Date Issued: 2021
Photophysicochemical properties and in vitro photodynamic therapy activities of zinc phthalocyanine conjugates with biomolecules and single-walled carbon nanotubes
- Authors: Ogbodu, Racheal O
- Date: 2015
- Subjects: Photochemotherapy , Phthalocyanines , Biomolecules
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4544 , http://hdl.handle.net/10962/d1017924
- Description: The synthesis, photophysicochemcial properties, in vitro dark toxicity and photodynamic therapy (PDT) activities of different derivatives of zinc phthalocyanine (ZnPc) conjugates with biomolecules (folic acid, bovine serum albumin (BSA), ascorbic acid, uridine or spermine) and single-walled carbon nanotubes (SWCNTs) are presented in this work. The fluorescence quantum yields (ΦF) (Subscript F) of the ZnPc derivatives or ZnPc-biomolecule conjugates remained relatively the same as compared to the precursor Pcs. Slight increases were observed in the ΦF (Subscript F) values of conjugates containing substituents such as pyrene, folic acid or BSA with intrinsic fluorescence properties. The triplet quantum yield (ΦT ) (Subscript T) values for some ZnPc conjugates increases compared to the precursor ZnPcs due to extended π conjugation (for the conjugate with pyrene) and the presence of phenyl ring that support spin-orbit charge transfer intersystem crossing to triplet state. While some conjugates showed decreases in the ΦT (Subscript T) values compared to precursor ZnPcs due to the presence of substituents that could quench photo-excited state properties. The singlet oxygen quantum yield (ΦΔ ) values follow the trends of the triplet quantum yield values. The conjugates containing BSA also show increases in the ΦΔ values without corresponding increases in ΦT (Subscript T) values due to the ability of BSA to generate free radicals including singlet oxygen. The presence of SWCNTs decreases the photophysicochemcial properties of some ZnPc-SWCNT conjugates compared to the precursor ZnPcs due to photo-induced electron transfer from an excited Pc complex (electron donor) to SWCNTs (electron acceptor). However, increases were observed in some ZnPc-SWCNT conjugates as a result of fast charge recombination process due to highly short-lived radical ion pair produced. These phenomena affected the ΦF (Suscript F) values, ΦT (Suscript T) values, and the ΦΔ values. Increases or decreases in ΦT (Suscript T) values resulted in corresponding increases or decreases in ΦΔ values
- Full Text:
- Date Issued: 2015
- Authors: Ogbodu, Racheal O
- Date: 2015
- Subjects: Photochemotherapy , Phthalocyanines , Biomolecules
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4544 , http://hdl.handle.net/10962/d1017924
- Description: The synthesis, photophysicochemcial properties, in vitro dark toxicity and photodynamic therapy (PDT) activities of different derivatives of zinc phthalocyanine (ZnPc) conjugates with biomolecules (folic acid, bovine serum albumin (BSA), ascorbic acid, uridine or spermine) and single-walled carbon nanotubes (SWCNTs) are presented in this work. The fluorescence quantum yields (ΦF) (Subscript F) of the ZnPc derivatives or ZnPc-biomolecule conjugates remained relatively the same as compared to the precursor Pcs. Slight increases were observed in the ΦF (Subscript F) values of conjugates containing substituents such as pyrene, folic acid or BSA with intrinsic fluorescence properties. The triplet quantum yield (ΦT ) (Subscript T) values for some ZnPc conjugates increases compared to the precursor ZnPcs due to extended π conjugation (for the conjugate with pyrene) and the presence of phenyl ring that support spin-orbit charge transfer intersystem crossing to triplet state. While some conjugates showed decreases in the ΦT (Subscript T) values compared to precursor ZnPcs due to the presence of substituents that could quench photo-excited state properties. The singlet oxygen quantum yield (ΦΔ ) values follow the trends of the triplet quantum yield values. The conjugates containing BSA also show increases in the ΦΔ values without corresponding increases in ΦT (Subscript T) values due to the ability of BSA to generate free radicals including singlet oxygen. The presence of SWCNTs decreases the photophysicochemcial properties of some ZnPc-SWCNT conjugates compared to the precursor ZnPcs due to photo-induced electron transfer from an excited Pc complex (electron donor) to SWCNTs (electron acceptor). However, increases were observed in some ZnPc-SWCNT conjugates as a result of fast charge recombination process due to highly short-lived radical ion pair produced. These phenomena affected the ΦF (Suscript F) values, ΦT (Suscript T) values, and the ΦΔ values. Increases or decreases in ΦT (Suscript T) values resulted in corresponding increases or decreases in ΦΔ values
- Full Text:
- Date Issued: 2015
Synthesis of indium phthalocyanines for photodynamic antimicrobial chemotherapy and photo-oxidation of pollutants
- Authors: Sindelo, Azole
- Date: 2019
- Subjects: Phthalocyanines , Azo dyes , Indium compounds , Photochemotherapy , Nanoparticles , Photodegradation , Pollutants , Water -- Purification
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67581 , vital:29116
- Description: Indium (III) octacarboxyl phthalocyanine (ClInOCPc) alone and when conjugated to magnetic nanoparticles (MNP-ClInOCPc), 2(3),9(10),16(17),23(24)-octapyridylsulfanyl phthalocyaninato chloroindium (III) (ClInOPyPc) and its quaternized derivative 2(3),9(10),16(17),23(24)-octamethylpyridylsulfanyl phthalocyaninato chloroindium (III) (ClInOMePyPc) were synthesized. All Pcs were tested for both photodynamic antimicrobial chemotherapy (PACT) of an unknown water sample and photo-degradation of methyl red (MR). The singlet quantum yield (ΦΔ) for the ClInOCPc and MNP-ClInOCPc in PAN polymer fibers were 0.36 and 0.20 respectively using ADMA as a quencher in water. The photo-inactivation of bacteria in a water sample with unknown microbes was tested, with the MNP-ClInOCPc inactivating 90.6 % of the microbes and the ClInOCPc with 84.8 %. When embedded to the polymer, there was 48% bacterial clearance for ClInOCPc and 64% clearance for the MNP-ClInOCPc. The rate of degradation of MR increased with decrease of the MR concentration, with the MNP-ClInOCPc having the fastest rate. For ClInOPyPc and ClInOMePyPc, the singlet quantum yields were 0.46 and 0.33 in dimethylformamide (DMF), respectively. The PACT activity of ClInOMePyPc (containing 8 positive charges) was compared to those of 9(10),16(17),23(24)-tri-N-methyl-4-pyridylsulfanyl-2(3)-(4-aminophenoxy) phthalocyaninato chloro indium (III) triiodide (1) (containing 3 positive charges) and 2-[4-(N-methylpyridyloxy) phthalocyaninato] chloroindium (III) iodide (2) (containing 4 positive charges). When comparing ClInOMePyPc, 1 and 2, the largest log reduction for E. coli were obtained for complex 2 containing four positive charges hence showing it is not always the charge that determines the PACT activity, but the bridging atom in the phthalocyanine plays a role.
- Full Text:
- Date Issued: 2019
- Authors: Sindelo, Azole
- Date: 2019
- Subjects: Phthalocyanines , Azo dyes , Indium compounds , Photochemotherapy , Nanoparticles , Photodegradation , Pollutants , Water -- Purification
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67581 , vital:29116
- Description: Indium (III) octacarboxyl phthalocyanine (ClInOCPc) alone and when conjugated to magnetic nanoparticles (MNP-ClInOCPc), 2(3),9(10),16(17),23(24)-octapyridylsulfanyl phthalocyaninato chloroindium (III) (ClInOPyPc) and its quaternized derivative 2(3),9(10),16(17),23(24)-octamethylpyridylsulfanyl phthalocyaninato chloroindium (III) (ClInOMePyPc) were synthesized. All Pcs were tested for both photodynamic antimicrobial chemotherapy (PACT) of an unknown water sample and photo-degradation of methyl red (MR). The singlet quantum yield (ΦΔ) for the ClInOCPc and MNP-ClInOCPc in PAN polymer fibers were 0.36 and 0.20 respectively using ADMA as a quencher in water. The photo-inactivation of bacteria in a water sample with unknown microbes was tested, with the MNP-ClInOCPc inactivating 90.6 % of the microbes and the ClInOCPc with 84.8 %. When embedded to the polymer, there was 48% bacterial clearance for ClInOCPc and 64% clearance for the MNP-ClInOCPc. The rate of degradation of MR increased with decrease of the MR concentration, with the MNP-ClInOCPc having the fastest rate. For ClInOPyPc and ClInOMePyPc, the singlet quantum yields were 0.46 and 0.33 in dimethylformamide (DMF), respectively. The PACT activity of ClInOMePyPc (containing 8 positive charges) was compared to those of 9(10),16(17),23(24)-tri-N-methyl-4-pyridylsulfanyl-2(3)-(4-aminophenoxy) phthalocyaninato chloro indium (III) triiodide (1) (containing 3 positive charges) and 2-[4-(N-methylpyridyloxy) phthalocyaninato] chloroindium (III) iodide (2) (containing 4 positive charges). When comparing ClInOMePyPc, 1 and 2, the largest log reduction for E. coli were obtained for complex 2 containing four positive charges hence showing it is not always the charge that determines the PACT activity, but the bridging atom in the phthalocyanine plays a role.
- Full Text:
- Date Issued: 2019
Nonlinear optical responses of phthalocyanines in the presence of nanomaterials or when embedded in polymeric materials
- Authors: Bankole, Owolabi Mutolib
- Date: 2017
- Subjects: Phthalocyanines , Phthalocyanines -- Optical properties , Alkynes , Triazoles , Nonlinear optics , Photochemistry , Complex compounds , Amines , Mercaptopyridine
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/45794 , vital:25548
- Description: This work describes the synthesis, photophysical and nonlinear optical characterizations of alkynyl Pcs (1, 2, 3, 8 and 9), 1,2,3-triazole ZnPc (4), mercaptopyridine Pcs (5, 6 and 7) and amino Pcs (10 and 11). Complexes 1, 2, 4, 7, 8, 9 and 11 were newly synthesized and characterized using techniques including 1H-NMR, MALDI-TOF, UV-visible spectrophotometry, FTIR and elemental analysis. The results of the characterizations were in good agreement with their molecular structures, and confirmed the purity of the new molecules. Complex 10 was covalently linked to pristine graphene (GQDs), nitrogen- doped (NGQDs), and sulfur-nitrogen co-doped (SNGQDs) graphene quantum dots; gold nanoparticles (AuNPs); poly(acrylic acid) (PAA); Fe3O4@Ag core-shell and Fe3O4- Ag hybrid nanoparticles via covalent bonding. Complex 11 was linked to Agx Auy alloy nanoparticles via NH2-Au and/or Au-S bonding, 2 and 3 were linked to gold nanoparticles (AuNPs) via clicked reactions. Evidence of successful conjugation of 2, 3, 10 and 11 to nanomaterials was revealed within the UV-vis, EDS, TEM, XRD and XPS spectra. Optical limiting (OL) responses of the samples were evaluated using open aperture Z-scan technique at 532 nm and 10 ns radiation in solution or when embedded in polymer mixtures. The analyses of the Z-scan data for the studied samples did fit to a two-photon absorption mechanism (2PA), but the Pcs and Pc-nanomaterial or polymer composites also possess the multi-photon absorption mechanisms aided by the triplet-triplet population to have reverse saturable absorption (RSA) occur. Phthalocyanines doped in polymer matrices showed larger nonlinear absorption coefficients (ßeff), third-order susceptibility (Im [x(3)]) and second-order hyperpolarizability (y), with an accompanying low intensity threshold (Ium) than in solution. Aggregation in DMSO negatively affected NLO behaviour of Pcs (8 as a case study) at low laser power, and improved at relatively higher laser power. Heavy atom-substituted Pcs (6) enhanced NLO and OL properties than lighter atoms such as 5 and 7. Direct relationship between enhanced photophysical properties and nonlinear effects favoured by excited triplet absorption of the 2, 3, 10 and 11 in presence of nanomaterials was established. Major factor responsible for the enhanced nonlinearities of 10 in the presence of NGQDs and SNGQDs were fully described and attributed to the surface defects caused by the presence of heteroatoms such as nitrogen and sulfur. The studies showed that phthalocyanines-nanomaterial composites were useful in applications such as optical switching, pulse compressor and laser pulse narrowing.
- Full Text:
- Date Issued: 2017
- Authors: Bankole, Owolabi Mutolib
- Date: 2017
- Subjects: Phthalocyanines , Phthalocyanines -- Optical properties , Alkynes , Triazoles , Nonlinear optics , Photochemistry , Complex compounds , Amines , Mercaptopyridine
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/45794 , vital:25548
- Description: This work describes the synthesis, photophysical and nonlinear optical characterizations of alkynyl Pcs (1, 2, 3, 8 and 9), 1,2,3-triazole ZnPc (4), mercaptopyridine Pcs (5, 6 and 7) and amino Pcs (10 and 11). Complexes 1, 2, 4, 7, 8, 9 and 11 were newly synthesized and characterized using techniques including 1H-NMR, MALDI-TOF, UV-visible spectrophotometry, FTIR and elemental analysis. The results of the characterizations were in good agreement with their molecular structures, and confirmed the purity of the new molecules. Complex 10 was covalently linked to pristine graphene (GQDs), nitrogen- doped (NGQDs), and sulfur-nitrogen co-doped (SNGQDs) graphene quantum dots; gold nanoparticles (AuNPs); poly(acrylic acid) (PAA); Fe3O4@Ag core-shell and Fe3O4- Ag hybrid nanoparticles via covalent bonding. Complex 11 was linked to Agx Auy alloy nanoparticles via NH2-Au and/or Au-S bonding, 2 and 3 were linked to gold nanoparticles (AuNPs) via clicked reactions. Evidence of successful conjugation of 2, 3, 10 and 11 to nanomaterials was revealed within the UV-vis, EDS, TEM, XRD and XPS spectra. Optical limiting (OL) responses of the samples were evaluated using open aperture Z-scan technique at 532 nm and 10 ns radiation in solution or when embedded in polymer mixtures. The analyses of the Z-scan data for the studied samples did fit to a two-photon absorption mechanism (2PA), but the Pcs and Pc-nanomaterial or polymer composites also possess the multi-photon absorption mechanisms aided by the triplet-triplet population to have reverse saturable absorption (RSA) occur. Phthalocyanines doped in polymer matrices showed larger nonlinear absorption coefficients (ßeff), third-order susceptibility (Im [x(3)]) and second-order hyperpolarizability (y), with an accompanying low intensity threshold (Ium) than in solution. Aggregation in DMSO negatively affected NLO behaviour of Pcs (8 as a case study) at low laser power, and improved at relatively higher laser power. Heavy atom-substituted Pcs (6) enhanced NLO and OL properties than lighter atoms such as 5 and 7. Direct relationship between enhanced photophysical properties and nonlinear effects favoured by excited triplet absorption of the 2, 3, 10 and 11 in presence of nanomaterials was established. Major factor responsible for the enhanced nonlinearities of 10 in the presence of NGQDs and SNGQDs were fully described and attributed to the surface defects caused by the presence of heteroatoms such as nitrogen and sulfur. The studies showed that phthalocyanines-nanomaterial composites were useful in applications such as optical switching, pulse compressor and laser pulse narrowing.
- Full Text:
- Date Issued: 2017
Photo-physicochemical studies and photodynamic therapy activity of indium and gallium phthalocyanines
- Tshangana, Charmaine Sesethu
- Authors: Tshangana, Charmaine Sesethu
- Date: 2015
- Subjects: Quantum dots , Nanoparticles , Photochemotherapy , Phthalocyanines
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4548 , http://hdl.handle.net/10962/d1017928
- Description: The potential toxicity of seven different types of quantum dots without shell (L-cysteine-CdTe, TGA-CdTe, MPA-CdTe, TGA-CdSe) and with the shell (GSH-CdSe@ZnS, GSH-CdTe@ZnS,) with different capping agents were evaluated. The growth inhibitory effects of the various quantum dots on human pancreatic BON cancerous cells were determined. The least cytotoxic of the various quantum dots synthesized and the one displaying the lowest growth inhibitory potential and no embryotoxicity was determined to be the GSH-CdSe@ZnS quantum dots. The GSH-CdSe@ZnS quantum dots were then conjugated to gallium, aluminium and indium octacarboxy phthalocyanine and the photophysical behaviour of the conjugates studied for potential use in photodynamic therapy and imaging applications. The sizes, morphology, thermal stability and confirmation of successful conjugation was determined using X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR), respectively. The study was extended by conjugating amino functionalized magnetic nanoparticles (Fe₃O₄) to indium octacarboxy phthalocyanine to study the photophysical behaviour of the conjugate as a potential bi-functional anti-cancer agent (hyperthermia and photodynamic therapy applications). A three-in-one multifunctional nanocomposite comprising of the quantum dots, magnetic nanoparticles and indium octacarboxy phthalocyanine was developed with the aim of developing a multifunctional composite that is able detect, monitor and treat cancer. All conjugates showed improved and enhanced photophysical behaviour. Finally, GSH-CdSe@ZnS conjugated to aluminium octacarboxy phthalocyanine was applied in human pancreatic carcinoid BON cells. The conjugates induced cell death dose-dependently.
- Full Text:
- Date Issued: 2015
- Authors: Tshangana, Charmaine Sesethu
- Date: 2015
- Subjects: Quantum dots , Nanoparticles , Photochemotherapy , Phthalocyanines
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4548 , http://hdl.handle.net/10962/d1017928
- Description: The potential toxicity of seven different types of quantum dots without shell (L-cysteine-CdTe, TGA-CdTe, MPA-CdTe, TGA-CdSe) and with the shell (GSH-CdSe@ZnS, GSH-CdTe@ZnS,) with different capping agents were evaluated. The growth inhibitory effects of the various quantum dots on human pancreatic BON cancerous cells were determined. The least cytotoxic of the various quantum dots synthesized and the one displaying the lowest growth inhibitory potential and no embryotoxicity was determined to be the GSH-CdSe@ZnS quantum dots. The GSH-CdSe@ZnS quantum dots were then conjugated to gallium, aluminium and indium octacarboxy phthalocyanine and the photophysical behaviour of the conjugates studied for potential use in photodynamic therapy and imaging applications. The sizes, morphology, thermal stability and confirmation of successful conjugation was determined using X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR), respectively. The study was extended by conjugating amino functionalized magnetic nanoparticles (Fe₃O₄) to indium octacarboxy phthalocyanine to study the photophysical behaviour of the conjugate as a potential bi-functional anti-cancer agent (hyperthermia and photodynamic therapy applications). A three-in-one multifunctional nanocomposite comprising of the quantum dots, magnetic nanoparticles and indium octacarboxy phthalocyanine was developed with the aim of developing a multifunctional composite that is able detect, monitor and treat cancer. All conjugates showed improved and enhanced photophysical behaviour. Finally, GSH-CdSe@ZnS conjugated to aluminium octacarboxy phthalocyanine was applied in human pancreatic carcinoid BON cells. The conjugates induced cell death dose-dependently.
- Full Text:
- Date Issued: 2015
Effect of substituents on the photophysical properties and nonlinear optical properties of asymmetrical zinc(II) phthalocyanine when conjugated to semiconductor quantum dots
- Authors: Mgidlana, Sithi
- Date: 2019
- Subjects: Nonlinear optics , Quantum dots , Phthalocyanines , Zinc
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/97152 , vital:31404
- Description: Various characterization techniques have been used to characterize the synthesized asymmetrical zinc phthalocyanines (ZnPc) derivatives. Techniques include Ultraviolet-visible (UV-vis) spectrophotometry, matrix assisted laser desorption time of flight mass spectrometry (MALD-TOF MS), proton nuclear magnetic resonance (1H-NMR), elemental analysis and Fourier-transform infra-red spectroscopy (FT-IR). The complexes are covalently linked to core/shell and core/shell/shell semiconductor quantum dots (SQDs) via amide bond formation. Photophysical properties of complexes improved in the presence of semiconductor quantum dots (SQDs). SQDs contain cadmium/telluride (CdTe) as core, coated in the first shell with zinc selenide (ZnSe) or zinc sulfide (ZnS) and with zinc oxide (ZnO) in second shell. The photophysical properties of the phthalocyanine (Pc) complexes and their conjugates with SQDs are investigated in solution. Triplet quantum yields of complexes improved in the presence of semiconductor quantum dots. The optical limiting behaviour of the Pc complexes and conjugates are assessed using the open aperture Z–scan technique at laser excitation wavelength of 532 nm with 10 ns pulse. Pcs complexes showed good nonlinear optical response with higher nonlinear absorption coefficient. The conjugates afforded higher nonlinear absorption coefficient than Pc complexes alone.
- Full Text:
- Date Issued: 2019
- Authors: Mgidlana, Sithi
- Date: 2019
- Subjects: Nonlinear optics , Quantum dots , Phthalocyanines , Zinc
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/97152 , vital:31404
- Description: Various characterization techniques have been used to characterize the synthesized asymmetrical zinc phthalocyanines (ZnPc) derivatives. Techniques include Ultraviolet-visible (UV-vis) spectrophotometry, matrix assisted laser desorption time of flight mass spectrometry (MALD-TOF MS), proton nuclear magnetic resonance (1H-NMR), elemental analysis and Fourier-transform infra-red spectroscopy (FT-IR). The complexes are covalently linked to core/shell and core/shell/shell semiconductor quantum dots (SQDs) via amide bond formation. Photophysical properties of complexes improved in the presence of semiconductor quantum dots (SQDs). SQDs contain cadmium/telluride (CdTe) as core, coated in the first shell with zinc selenide (ZnSe) or zinc sulfide (ZnS) and with zinc oxide (ZnO) in second shell. The photophysical properties of the phthalocyanine (Pc) complexes and their conjugates with SQDs are investigated in solution. Triplet quantum yields of complexes improved in the presence of semiconductor quantum dots. The optical limiting behaviour of the Pc complexes and conjugates are assessed using the open aperture Z–scan technique at laser excitation wavelength of 532 nm with 10 ns pulse. Pcs complexes showed good nonlinear optical response with higher nonlinear absorption coefficient. The conjugates afforded higher nonlinear absorption coefficient than Pc complexes alone.
- Full Text:
- Date Issued: 2019
Functionalized Ru(II) polypyridines and phthalocyanines: Potential dyes for dye-sensitized solar cells(DSSCs)
- Adeloye, Adewale Olufunsho https://orcid.org/0000-0003-1736-5738
- Authors: Adeloye, Adewale Olufunsho https://orcid.org/0000-0003-1736-5738
- Date: 2011-01
- Subjects: Phthalocyanines , Dye-sensitized solar cells
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10353/24365 , vital:62645
- Description: This study describes the design, synthesis, characterization and preliminary investigation of the solar-to-electrical energy conversion efficiency of ruthenium(II) functionalized polypyridine and phthalocyanine complexes with extended π-conjugation. Polypyridinyl functionalized with anthracene, 2,3-dimethylacrylic acid and 1-methoxy-1-buten-3-yne were synthesized and characterized by infrared, UV-Vis, photoluminescence, 1H and 13C NMR and elemental analysis. The functionalized polypyridine molecules were used to synthesize various ruthenium(II) homoleptic/heteroleptic and/or heteronuclear complexes and their photophysical and electrochemical properties evaluated. The preliminary results of the solar-to-electrical conversion efficiencies of some synthesized Ru(II) polypyridyl complexes were presented in chapter 5. It was found out as expected that the ruthenium(II) polypyridine complexes containing either heteronuclear polypyridine ligands or their thiocyanate analogues of the types [Ru(L1)2L2(PF6)2], [RuL1(L2)2(PF6)2] and [RuL1L2(NCS)2], showed better photophysical properties (red-shifted metal-to-ligand charge-transfer (MLCT) transitions concomitant with enhanced molar extinction coefficients), luminescence and interesting electrochemical redox properties than those containing homonuclear ligand types [Ru(L1)3(PF6)2]. The ruthenium(II) anthracenyl functionalized phthalocyanine complexes which were obtained by electrophilic aromatic substitution reactions in the peripheral positions gave good solubility properties in various organic solvents and also showed interesting near infrared absorption and electroredox characteristics. Cyclic and square wave voltammetries of these complexes revealed major redox processes and the numbers of electron(s) transfer were determined by chronocoulometry. It was established that a mono- and/or multi-electronic transfer reactions can occur in the various ruthenium(II) complexes. The photophysical properties of some complexes showed them to be better and promising candidates in the design of chemosensors, organic light emitting diodes (OLEDs) and as photosensitizers, while their redox-active natures make them potential mediators in electron-transfer for various photochemical processes. However, due to low surface concentration and/or adsorption of some tested complexes on TiO2 semiconductor nanocrystalline particle, low currents were generated and the highest solar-to- electrical conversion efficiency recorded in this study was 0.10 percent. , Thesis (PhD) -- Faculty of Science and Agriculture, 2011
- Full Text:
- Date Issued: 2011-01
- Authors: Adeloye, Adewale Olufunsho https://orcid.org/0000-0003-1736-5738
- Date: 2011-01
- Subjects: Phthalocyanines , Dye-sensitized solar cells
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10353/24365 , vital:62645
- Description: This study describes the design, synthesis, characterization and preliminary investigation of the solar-to-electrical energy conversion efficiency of ruthenium(II) functionalized polypyridine and phthalocyanine complexes with extended π-conjugation. Polypyridinyl functionalized with anthracene, 2,3-dimethylacrylic acid and 1-methoxy-1-buten-3-yne were synthesized and characterized by infrared, UV-Vis, photoluminescence, 1H and 13C NMR and elemental analysis. The functionalized polypyridine molecules were used to synthesize various ruthenium(II) homoleptic/heteroleptic and/or heteronuclear complexes and their photophysical and electrochemical properties evaluated. The preliminary results of the solar-to-electrical conversion efficiencies of some synthesized Ru(II) polypyridyl complexes were presented in chapter 5. It was found out as expected that the ruthenium(II) polypyridine complexes containing either heteronuclear polypyridine ligands or their thiocyanate analogues of the types [Ru(L1)2L2(PF6)2], [RuL1(L2)2(PF6)2] and [RuL1L2(NCS)2], showed better photophysical properties (red-shifted metal-to-ligand charge-transfer (MLCT) transitions concomitant with enhanced molar extinction coefficients), luminescence and interesting electrochemical redox properties than those containing homonuclear ligand types [Ru(L1)3(PF6)2]. The ruthenium(II) anthracenyl functionalized phthalocyanine complexes which were obtained by electrophilic aromatic substitution reactions in the peripheral positions gave good solubility properties in various organic solvents and also showed interesting near infrared absorption and electroredox characteristics. Cyclic and square wave voltammetries of these complexes revealed major redox processes and the numbers of electron(s) transfer were determined by chronocoulometry. It was established that a mono- and/or multi-electronic transfer reactions can occur in the various ruthenium(II) complexes. The photophysical properties of some complexes showed them to be better and promising candidates in the design of chemosensors, organic light emitting diodes (OLEDs) and as photosensitizers, while their redox-active natures make them potential mediators in electron-transfer for various photochemical processes. However, due to low surface concentration and/or adsorption of some tested complexes on TiO2 semiconductor nanocrystalline particle, low currents were generated and the highest solar-to- electrical conversion efficiency recorded in this study was 0.10 percent. , Thesis (PhD) -- Faculty of Science and Agriculture, 2011
- Full Text:
- Date Issued: 2011-01
Phthalocyanine-nanoparticle conjugates for photodynamic therapy of cancer and phototransformation of organic pollutants
- Authors: Khoza, Phindile Brenda
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Photochemotherapy , Cancer -- Chemotherapy , Zinc oxide , Photocatalysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4538 , http://hdl.handle.net/10962/d1017918
- Description: The synthesis and extensive spectroscopical characterization of novel phthalocyanines are reported. The new compounds were characterized by elemental analysis, FT-IR, ¹HNMR, mass spectrometry and UV–Vis spectroscopy. The new phthalocyanines showed remarkable photophysicochemical behaviour. The novel phthalocyanines were then conjugated to nanoparticles, silver and ZnO. The coupling of the novel Pcs to nanoparticles was through covalent bonding and ligand exchange. These conjugates were supported onto electrospun polystyrene fibers and chitosan microbeads for use as photocatalysts. The efficiency of the immobilized Pcs and Pc-nanoparticles was assessed by the phototrasfromation of organic pollutants, methyl orange and Rhodamine 6G as model dyes. Upon conjugating phthalocyanines to nanoparticles, there was a great increase in the rate of photodegradation of the model dyes. The photodynamic activity of the novel phthalocyanines upon conjugating to nanoparticles and selected targeting agents is also reported. The targeting agents employed in this study are folic acid and polylysine. Conjugating the phthalocyanines to folic acid or polylysine improved the solubility of the phthalocyanines in aqueous media. The potency of the conjugates was investigated on breast (MCF-7), prostate and melanoma cancer cell lines. The phthalocyanines showed no toxicity in the absence of light. However, upon illumination, a concentration dependent cellular decrease was observed.
- Full Text:
- Date Issued: 2015
- Authors: Khoza, Phindile Brenda
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Photochemotherapy , Cancer -- Chemotherapy , Zinc oxide , Photocatalysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4538 , http://hdl.handle.net/10962/d1017918
- Description: The synthesis and extensive spectroscopical characterization of novel phthalocyanines are reported. The new compounds were characterized by elemental analysis, FT-IR, ¹HNMR, mass spectrometry and UV–Vis spectroscopy. The new phthalocyanines showed remarkable photophysicochemical behaviour. The novel phthalocyanines were then conjugated to nanoparticles, silver and ZnO. The coupling of the novel Pcs to nanoparticles was through covalent bonding and ligand exchange. These conjugates were supported onto electrospun polystyrene fibers and chitosan microbeads for use as photocatalysts. The efficiency of the immobilized Pcs and Pc-nanoparticles was assessed by the phototrasfromation of organic pollutants, methyl orange and Rhodamine 6G as model dyes. Upon conjugating phthalocyanines to nanoparticles, there was a great increase in the rate of photodegradation of the model dyes. The photodynamic activity of the novel phthalocyanines upon conjugating to nanoparticles and selected targeting agents is also reported. The targeting agents employed in this study are folic acid and polylysine. Conjugating the phthalocyanines to folic acid or polylysine improved the solubility of the phthalocyanines in aqueous media. The potency of the conjugates was investigated on breast (MCF-7), prostate and melanoma cancer cell lines. The phthalocyanines showed no toxicity in the absence of light. However, upon illumination, a concentration dependent cellular decrease was observed.
- Full Text:
- Date Issued: 2015
Photophysicochemical properties of aluminium phthalocyanine-platinum conjugates
- Authors: Malinga, Nduduzo Nkanyiso
- Date: 2013 , 2013-04-05
- Subjects: Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4285 , http://hdl.handle.net/10962/d1002954 , Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Description: The combination of chemotherapy and photodynamic therapy was investigated by synthesis and characterization of octacarboxy phthalocyanine covalent conjugates with platinum complexes. This work presents the synthesis, characterization and photophysicochemical properties of aluminium (diaquaplatinum) octacarboxyphthalocyanine and aluminium (diammine) octacarboxyphthalocyanine. The conjugates were prepared by conjugating aluminium octacarboxy phthalocyanine with potassium tetrachloro platinate to yield aluminium tetrakis and trikis (diaquaplatinum) octacarboxy phthalocyanine. The aluminium octacarboxy phthalocyanine was also conjugated with cis-diamminedichloroplatinum to yield aluminium bis and tris (diaquaplatinum) octacarboxy phthalocyanine. From the characterization of the conjugates it was discovered that the aluminium (diaquaplatinum) octacarboxy phthalocyanine had formed platinum nanoparticles with the Pc acting as a capping agent. The triplet lifetimes decreased with the increasing number of platinum complexesconjugated to the Pc. The heavy atom effect improved the overall photophysicochemical properties.
- Full Text:
- Date Issued: 2013
- Authors: Malinga, Nduduzo Nkanyiso
- Date: 2013 , 2013-04-05
- Subjects: Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4285 , http://hdl.handle.net/10962/d1002954 , Phthalocyanines , Photochemistry , Photochemotherapy , Aluminium , Platinum , Nanoparticles , Cancer -- Photochemotherapy
- Description: The combination of chemotherapy and photodynamic therapy was investigated by synthesis and characterization of octacarboxy phthalocyanine covalent conjugates with platinum complexes. This work presents the synthesis, characterization and photophysicochemical properties of aluminium (diaquaplatinum) octacarboxyphthalocyanine and aluminium (diammine) octacarboxyphthalocyanine. The conjugates were prepared by conjugating aluminium octacarboxy phthalocyanine with potassium tetrachloro platinate to yield aluminium tetrakis and trikis (diaquaplatinum) octacarboxy phthalocyanine. The aluminium octacarboxy phthalocyanine was also conjugated with cis-diamminedichloroplatinum to yield aluminium bis and tris (diaquaplatinum) octacarboxy phthalocyanine. From the characterization of the conjugates it was discovered that the aluminium (diaquaplatinum) octacarboxy phthalocyanine had formed platinum nanoparticles with the Pc acting as a capping agent. The triplet lifetimes decreased with the increasing number of platinum complexesconjugated to the Pc. The heavy atom effect improved the overall photophysicochemical properties.
- Full Text:
- Date Issued: 2013
The electrocatalytic response of metallophthalocyanines when clicked to electrodes and to nanomaterials
- Authors: Mpeta, Lekhetho Simon
- Date: 2021
- Subjects: Phthalocyanines , Nanostructured materials , Electrocatalysis , Nanoparticles , Environmental chemistry , Electrodes , Organic wastes -- Purification
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/172191 , vital:42174 , 10.21504/10962/172191
- Description: Conjugates of nanomaterials and metallophthalocyanines (MPcs) have been prepared and their electrocatalytic activity studied. The prepared nanomaterials are zinc oxide and silver nanoparticles, reduced graphene oxide nanosheets and semiconductor quantum dots. The MPcs used in this work are cobalt (II) (1a), manganese(III) (1b) and iron (II) (1c) 2,9(10),16(17),23(24)- tetrakis 4-((4-ethynylbenzyl) oxy) phthalocyaninato, 2,9(10),16(17),23(24)- tetrakis(5-pentyn-oxy) cobalt (II) phthalocyaninato (2), 9(10),16(17),23(24)- tris-[4-tert-butylphenoxy)-2- (4-ethylbezyl-oxy) cobalt (II) phthalocyaninato (3), 9(10),16(17),23(24)- tris-[4-tertbutylphenoxy)-2-(pent-4yn-yloxy)] cobalt (II) phthalocyaninato (4), cobalt (II) (5a) and manganese (III) (5b) 2,9(10),16(17),23(24)- tetrakis [4-(4-(5-chloro-1H-benzo [d]imidazol-2-yl)phenoxy] phthalocyaninato and 9(10),16(17),23(24)- tris tert butyl phenoxy- 2- [4-(4-(5-chloro-1H-benzo[d]imidazole-2-yl)phenoxy] cobalt (II) phthalocyaninato (6). Some of these MPcs (1a, 3 and 4) were directly clicked on azide grafted electrode, while some (1b, 1c, 2, 5a and 5b) were clicked to azide functionalised nanomaterials and then drop-dried on the electrodes. One phthalocyanine (5b) was drop-dried on the electrode then silver nanoparticles were electrodeposited on it taking advantage of metal-N bond. Scanning electrochemical microscopy, voltammetry, chronoamperometry, electrochemical impedance spectroscopy are among electrochemical methods used to characterise modified electrodes. Transmission electron microscopy, X-ray photoelectron spectroscopy, Xray diffractometry, Raman spectroscopy and infrared spectroscopy were employed to study surface functionalities, morphology and topography of the nanomaterials and complexes. Electrocatalytic activity of the developed materials were studied towards oxidation of 2-mercaptoethanol, hydrazine and hydrogen peroxide while the reduction study was based on oxygen and hydrogen peroxide. In general, the conjugates displayed superior catalytic activity when compared to individual materials. Complex 2 alone and when conjugated to zinc oxide nanoparticles were studied for their nonlinear optical behaviour. And the same materials were explored for their hydrazine detection capability. The aim of this study was to develop sensitive, selective and affordable sensors for selected organic waste pollutants. Conjugates were found to achieve the aim of the study compared to when individual materials were employed.
- Full Text:
- Date Issued: 2021
- Authors: Mpeta, Lekhetho Simon
- Date: 2021
- Subjects: Phthalocyanines , Nanostructured materials , Electrocatalysis , Nanoparticles , Environmental chemistry , Electrodes , Organic wastes -- Purification
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/172191 , vital:42174 , 10.21504/10962/172191
- Description: Conjugates of nanomaterials and metallophthalocyanines (MPcs) have been prepared and their electrocatalytic activity studied. The prepared nanomaterials are zinc oxide and silver nanoparticles, reduced graphene oxide nanosheets and semiconductor quantum dots. The MPcs used in this work are cobalt (II) (1a), manganese(III) (1b) and iron (II) (1c) 2,9(10),16(17),23(24)- tetrakis 4-((4-ethynylbenzyl) oxy) phthalocyaninato, 2,9(10),16(17),23(24)- tetrakis(5-pentyn-oxy) cobalt (II) phthalocyaninato (2), 9(10),16(17),23(24)- tris-[4-tert-butylphenoxy)-2- (4-ethylbezyl-oxy) cobalt (II) phthalocyaninato (3), 9(10),16(17),23(24)- tris-[4-tertbutylphenoxy)-2-(pent-4yn-yloxy)] cobalt (II) phthalocyaninato (4), cobalt (II) (5a) and manganese (III) (5b) 2,9(10),16(17),23(24)- tetrakis [4-(4-(5-chloro-1H-benzo [d]imidazol-2-yl)phenoxy] phthalocyaninato and 9(10),16(17),23(24)- tris tert butyl phenoxy- 2- [4-(4-(5-chloro-1H-benzo[d]imidazole-2-yl)phenoxy] cobalt (II) phthalocyaninato (6). Some of these MPcs (1a, 3 and 4) were directly clicked on azide grafted electrode, while some (1b, 1c, 2, 5a and 5b) were clicked to azide functionalised nanomaterials and then drop-dried on the electrodes. One phthalocyanine (5b) was drop-dried on the electrode then silver nanoparticles were electrodeposited on it taking advantage of metal-N bond. Scanning electrochemical microscopy, voltammetry, chronoamperometry, electrochemical impedance spectroscopy are among electrochemical methods used to characterise modified electrodes. Transmission electron microscopy, X-ray photoelectron spectroscopy, Xray diffractometry, Raman spectroscopy and infrared spectroscopy were employed to study surface functionalities, morphology and topography of the nanomaterials and complexes. Electrocatalytic activity of the developed materials were studied towards oxidation of 2-mercaptoethanol, hydrazine and hydrogen peroxide while the reduction study was based on oxygen and hydrogen peroxide. In general, the conjugates displayed superior catalytic activity when compared to individual materials. Complex 2 alone and when conjugated to zinc oxide nanoparticles were studied for their nonlinear optical behaviour. And the same materials were explored for their hydrazine detection capability. The aim of this study was to develop sensitive, selective and affordable sensors for selected organic waste pollutants. Conjugates were found to achieve the aim of the study compared to when individual materials were employed.
- Full Text:
- Date Issued: 2021
Electrode surface modification using metallophthalocyanines and metal nanoparticles : electrocatalytic activity
- Authors: Maringa, Audacity
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Electrocatalysis , Scanning electron microscopy , X-ray photoelectron spectroscopy , Electrochemistry , Scanning electrochemical microscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4541 , http://hdl.handle.net/10962/d1017921
- Description: Metallophthalocyanines and metal nanoparticles were successfully synthesized and applied for the electrooxidation of amitrole, nitrite and hydrazine individually or when employed together. The synthesized materials were characterized using the following techniques: predominantly scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electrochemistry and scanning electrochemical microscopy (SECM). Different electrode modification methods were used to modify the glassy carbon substrates. The methods include adsorption, electrodeposition, electropolymerization and click chemistry. Modifying the glassy carbon substrate with MPc (electropolymerization) followed by metal nanoparticles (electrodeposition) or vice versa, made a hybrid modified surface that had efficient electron transfer. This was confirmed by electrochemical impedance studies with voltammetry measurements having lower detection potentials for the analytes. This work also describes for the first time the micropatterning of the glassy carbon substrate using the SECM tip. The substrate was electrografted with 4-azidobenzenediazonium salt and then the click reaction was performed using ethynylferrocene facilitated by Cu⁺ produced at the SECM tip. The SECM imaging was then used to show the clicked spot.
- Full Text:
- Date Issued: 2015
- Authors: Maringa, Audacity
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Electrocatalysis , Scanning electron microscopy , X-ray photoelectron spectroscopy , Electrochemistry , Scanning electrochemical microscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4541 , http://hdl.handle.net/10962/d1017921
- Description: Metallophthalocyanines and metal nanoparticles were successfully synthesized and applied for the electrooxidation of amitrole, nitrite and hydrazine individually or when employed together. The synthesized materials were characterized using the following techniques: predominantly scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electrochemistry and scanning electrochemical microscopy (SECM). Different electrode modification methods were used to modify the glassy carbon substrates. The methods include adsorption, electrodeposition, electropolymerization and click chemistry. Modifying the glassy carbon substrate with MPc (electropolymerization) followed by metal nanoparticles (electrodeposition) or vice versa, made a hybrid modified surface that had efficient electron transfer. This was confirmed by electrochemical impedance studies with voltammetry measurements having lower detection potentials for the analytes. This work also describes for the first time the micropatterning of the glassy carbon substrate using the SECM tip. The substrate was electrografted with 4-azidobenzenediazonium salt and then the click reaction was performed using ethynylferrocene facilitated by Cu⁺ produced at the SECM tip. The SECM imaging was then used to show the clicked spot.
- Full Text:
- Date Issued: 2015
Substituent effects on the electrocatalytic activity of cobalt phthalocyanine in the presence of graphene quantum dots
- Centane, Sixolile Sibongiseni
- Authors: Centane, Sixolile Sibongiseni
- Date: 2019
- Subjects: Phthalocyanines , Quantum dots , Electrocatalysis , Electrochemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67614 , vital:29121
- Description: The electrocatalytic activity of metallophthalocyanines derivatives is explored. Cobalt monocarboxyphenoxy phthalocyanine (1), cobalt tetracarboxyphenoxy phthalocyanine (2), cobalt tetraaminophenoxy phthalocyanine (3) and cobalt tris-(tert-butylphenoxy) monocarboxyphenoxy phthalocyanine (4) are the phthalocyanines employed in this work. The metallophthalocyanines were employed alone as well as in the presence of the carbon based graphene quantum dots. The electrocatalytic behaviour of functionalized GQDs is also explored herein. The catalytic processes studies were conducted on a glassy carbon electrode surface. Modification of the electrode was achieved by the adsorption method. The materials were adsorbed either alone, as premixed/covalently linked GQDs/Pc conjugates or sequentially. Sequentially adsorbed electrodes involved the phthalocyanines on top or beneath GQDs. Sequentially modified electrodes where the phthalocyanine had higher currents and low detection limits than when the phthalocyanine is underneath. Premixed conjugates showed better activity than the covalently formed conjugates. The nanomaterials synthesized and used in this work were characterized using transmission electron microscopy, UV-Vis spectroscopy, dynamic light scattering, Raman spectroscopy, X-ray diffraction, Atomic Force Microscopy and X-ray photoelectron spectroscopy. The modified electrodes were characterized using cyclic voltammetry and scanning electrochemical spectroscopy. The electrocatalytic activity of the modified electrodes towards the oxidation of hydrazine was evaluated using cyclic voltammetry and chronoamperometry. Superior catalytic activity was observed for the conjugates compared to that of the individual conjugates.
- Full Text:
- Date Issued: 2019
- Authors: Centane, Sixolile Sibongiseni
- Date: 2019
- Subjects: Phthalocyanines , Quantum dots , Electrocatalysis , Electrochemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67614 , vital:29121
- Description: The electrocatalytic activity of metallophthalocyanines derivatives is explored. Cobalt monocarboxyphenoxy phthalocyanine (1), cobalt tetracarboxyphenoxy phthalocyanine (2), cobalt tetraaminophenoxy phthalocyanine (3) and cobalt tris-(tert-butylphenoxy) monocarboxyphenoxy phthalocyanine (4) are the phthalocyanines employed in this work. The metallophthalocyanines were employed alone as well as in the presence of the carbon based graphene quantum dots. The electrocatalytic behaviour of functionalized GQDs is also explored herein. The catalytic processes studies were conducted on a glassy carbon electrode surface. Modification of the electrode was achieved by the adsorption method. The materials were adsorbed either alone, as premixed/covalently linked GQDs/Pc conjugates or sequentially. Sequentially adsorbed electrodes involved the phthalocyanines on top or beneath GQDs. Sequentially modified electrodes where the phthalocyanine had higher currents and low detection limits than when the phthalocyanine is underneath. Premixed conjugates showed better activity than the covalently formed conjugates. The nanomaterials synthesized and used in this work were characterized using transmission electron microscopy, UV-Vis spectroscopy, dynamic light scattering, Raman spectroscopy, X-ray diffraction, Atomic Force Microscopy and X-ray photoelectron spectroscopy. The modified electrodes were characterized using cyclic voltammetry and scanning electrochemical spectroscopy. The electrocatalytic activity of the modified electrodes towards the oxidation of hydrazine was evaluated using cyclic voltammetry and chronoamperometry. Superior catalytic activity was observed for the conjugates compared to that of the individual conjugates.
- Full Text:
- Date Issued: 2019