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
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
Nonlinear optical studies of phthalocyanines and their conjugates with nanomaterials
- Authors: Sanusi, Sikiru Olukayode
- Date: 2015
- Subjects: Phthalocyanines , Nonlinear optics
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4545 , http://hdl.handle.net/10962/d1017925
- Description: A number of metallophthalocyanines (MPcs) and metal-free phthalocyanines (H₂Pcs) have been synthesized and characterized using various characterization tools such as ¹H-NMR, TOF mass spectrometry, FT-IR, UV-visible spectrophotometry and CHNS elemental analysis. Some of the MPcs were covalently linked to nanomaterials such as silica nanoparticles (SiNPs), single-walled carbon nanotubes (SWCNTs), magnetite nanoparticles (MNPs) and quantum dots (QDs), or embedded in polymer thin-films using poly(methyl methacrylate) (PMMA) and poly(acrylic acid) (PAA) as the polymer sources. The phthalocyanine-nanomaterial composites (Pc-NMCs) were characterized with FT-IR, UV-visible spectrophotometry, transmission electron microscopy (TEM), thermogravimetry analysis and X-ray diffractometry. The nonlinear optical (NLO) properties (using the open-aperture Z-scan technique) of the MPcs and the Pc-NMCs were investigated. In general, most of the investigated MPcs showed good optical limiting behaviors, except for a few, like the non-peripherally-substituted 2-pyridyloxy phthalocyanines, which showed inhibited NLO response as a result of the ring-strain effects. The absence of a metal center was found to greatly reduce the inherent high nonlinearities expected of some of the phthalocyanine complexes. The octaphenoxy derivatives (61a – 61e) were found to exhibit reverse saturable absorption (RSA) that depends on the singlet-singlet transitions, hence making them less reliable optical limiters. The optical limiting properties of the MPcs were improved in the presence of nanomaterials such as the QDs, MNPs and SWCNTs, with MPc-QDs showing the best optical limiting behavior of the three. SiNPs have no significant effect on the optical limiting behavior of the MPcs. The optical limiting properties of the MPcs were greatly enhanced in the presence of PMMA or PAA polymers. The PAA polymer showed better optical limiting behavior compared to PMMA
- Full Text:
- Date Issued: 2015
- Authors: Sanusi, Sikiru Olukayode
- Date: 2015
- Subjects: Phthalocyanines , Nonlinear optics
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4545 , http://hdl.handle.net/10962/d1017925
- Description: A number of metallophthalocyanines (MPcs) and metal-free phthalocyanines (H₂Pcs) have been synthesized and characterized using various characterization tools such as ¹H-NMR, TOF mass spectrometry, FT-IR, UV-visible spectrophotometry and CHNS elemental analysis. Some of the MPcs were covalently linked to nanomaterials such as silica nanoparticles (SiNPs), single-walled carbon nanotubes (SWCNTs), magnetite nanoparticles (MNPs) and quantum dots (QDs), or embedded in polymer thin-films using poly(methyl methacrylate) (PMMA) and poly(acrylic acid) (PAA) as the polymer sources. The phthalocyanine-nanomaterial composites (Pc-NMCs) were characterized with FT-IR, UV-visible spectrophotometry, transmission electron microscopy (TEM), thermogravimetry analysis and X-ray diffractometry. The nonlinear optical (NLO) properties (using the open-aperture Z-scan technique) of the MPcs and the Pc-NMCs were investigated. In general, most of the investigated MPcs showed good optical limiting behaviors, except for a few, like the non-peripherally-substituted 2-pyridyloxy phthalocyanines, which showed inhibited NLO response as a result of the ring-strain effects. The absence of a metal center was found to greatly reduce the inherent high nonlinearities expected of some of the phthalocyanine complexes. The octaphenoxy derivatives (61a – 61e) were found to exhibit reverse saturable absorption (RSA) that depends on the singlet-singlet transitions, hence making them less reliable optical limiters. The optical limiting properties of the MPcs were improved in the presence of nanomaterials such as the QDs, MNPs and SWCNTs, with MPc-QDs showing the best optical limiting behavior of the three. SiNPs have no significant effect on the optical limiting behavior of the MPcs. The optical limiting properties of the MPcs were greatly enhanced in the presence of PMMA or PAA polymers. The PAA polymer showed better optical limiting behavior compared to PMMA
- Full Text:
- Date Issued: 2015
Nonlinear optical studies of phthalocyanines and triazatetrabenzcorroles in solution and in thin films
- Authors: Mkhize, Nhlakanipho Colin
- Date: 2015
- Subjects: Phthalocyanines , Thin films , Nonlinear optics , Phosphorus
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4542 , http://hdl.handle.net/10962/d1017922
- Description: This work presents photophysical and nonlinear optical properties of a novel Cd 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (CdOtBPPc) and compared with those of Pb 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (PbOtBPPc). For both the CdOtBPPc and PbOtBPPc, third order imaginary susceptibility and second order hyperpolarizability values were found to be within the limit set for good optical limiters. The Pcs were embedded in poly (methyl methacrylate) (PMMA) and poly(bisphenol A carbonate) (PBC) as thin films. The optical limiting values of the Pcs once embedded in film were found to be greatly improved and the limiting intensity of each film was well below the maximum threshold. Both PbOtBPPc and CdOtBPPc showed better optical limiting when embedded in PBC compared to PMMA. CdOtBPPc shows better nonlinear optical behaviour than PbOtBPPc in solution and as thin films, even though the former is aggregated in solution. Novel phosphorus triazatetrabenzcorroles (TBC) tetrasubstituted at the α- and β- and octa substituted at the β- positions of the peripheral fused benzene rings with t-butylphenoxy substituents were prepared and characterized. The effects of the substituents and the missing aza-nitrogen on the electronic structures and optical spectroscopy are investigated with TD-DFT calculations and MCD spectroscopy. The optical limiting properties were investigated to examine whether the lower symmetry that results from the direct pyrrole-pyrrole bond and hence the permanent dipole moment that is introduced result in higher safety thresholds, relative to the values that have been reported for phthalocyanines. The suitability of the compounds for singlet oxygen applications has also been examined. Novel phosphorus phthalocyanines, analogous to the triazatetrabenzcorroles were also investigated. Due to their high photodegradation quantum yield however, only the fluorescence quantum yields and lifetimes were able to be determined.
- Full Text:
- Date Issued: 2015
- Authors: Mkhize, Nhlakanipho Colin
- Date: 2015
- Subjects: Phthalocyanines , Thin films , Nonlinear optics , Phosphorus
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4542 , http://hdl.handle.net/10962/d1017922
- Description: This work presents photophysical and nonlinear optical properties of a novel Cd 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (CdOtBPPc) and compared with those of Pb 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (PbOtBPPc). For both the CdOtBPPc and PbOtBPPc, third order imaginary susceptibility and second order hyperpolarizability values were found to be within the limit set for good optical limiters. The Pcs were embedded in poly (methyl methacrylate) (PMMA) and poly(bisphenol A carbonate) (PBC) as thin films. The optical limiting values of the Pcs once embedded in film were found to be greatly improved and the limiting intensity of each film was well below the maximum threshold. Both PbOtBPPc and CdOtBPPc showed better optical limiting when embedded in PBC compared to PMMA. CdOtBPPc shows better nonlinear optical behaviour than PbOtBPPc in solution and as thin films, even though the former is aggregated in solution. Novel phosphorus triazatetrabenzcorroles (TBC) tetrasubstituted at the α- and β- and octa substituted at the β- positions of the peripheral fused benzene rings with t-butylphenoxy substituents were prepared and characterized. The effects of the substituents and the missing aza-nitrogen on the electronic structures and optical spectroscopy are investigated with TD-DFT calculations and MCD spectroscopy. The optical limiting properties were investigated to examine whether the lower symmetry that results from the direct pyrrole-pyrrole bond and hence the permanent dipole moment that is introduced result in higher safety thresholds, relative to the values that have been reported for phthalocyanines. The suitability of the compounds for singlet oxygen applications has also been examined. Novel phosphorus phthalocyanines, analogous to the triazatetrabenzcorroles were also investigated. Due to their high photodegradation quantum yield however, only the fluorescence quantum yields and lifetimes were able to be determined.
- Full Text:
- Date Issued: 2015
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
Photodynamic antimicrobial chemotherapy activities of porphyrin- and phthalocyanine-platinum nanoparticle conjugates
- Authors: Managa, Muthumuni Elizabeth
- Date: 2015
- Subjects: Photochemotherapy , Anti-infective agents , Porphyrins , Phthalocyanines , Platinum , Nanoparticles , Bioconjugates , Electrospinning
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4539 , http://hdl.handle.net/10962/d1017919
- Description: This work reports on the conjugation of differently shaped Pt nanoparticles (PtNPs) with ClGa(III) 5,10,15,20-tetrakis-(4-carboxyphenyl) porphyrin (1) as well as chloro - (5,10,15,20-tetrakis (4- (4- carboxy phenycarbonoimidoyl) phenyl) porphyrinato) gallium(III) (2) The work also reports on platination of dihydroxosilicon octacarboxyphthalocyanine (OH)₂SiOCPc (3) to give dihydroxosilicontris(diaquaplatinum)octacarboxyphthalocyanine (OH)₂SiOCPc(Pt)₃ (4). The resulting conjugates were used for photodynamic antimicrobial chemotherapy against S. aureus, E. coli and C. albicans. The degree of photo-inactivation is dependent on concentration of the conjugates, light dose (fluence) and illumination time. The log reduction obtained for 1 when conjugated to cubic PtNPs was 4.64 log (which indicate 99.99 percent of the bacteria have been killed), which is much higher than 3.94 log unit for 1-hexagonal PtNPs and 3.31 log units for 1-unshaped PtNPs. Complex 2 conjugated to hexagonal PtNPs showed 18 nm red shift in the Soret band when compared to 2 alone. Complex 2 and 2-hexagonal PtNPs as well showed promising photodynamic antimicrobial chemotherapy (PACT) activity against S. aureus, E. coli and C. albicans in solution where the log reduction obtained was 4.92, 3.76, and 3.95 respectively for 2-hexagonal PtNPs. The singlet oxygen quantum yields obtained were higher at 0.56 for 2-hexagonl PtNPs in DMF while that of 2 was 0.52 in the same solvent. This resulted in improved PACT activity for 2-hexagonal PtNPs compared to 2. Complex 4 showed slight blue shifting of the absorption spectrum when compared to complex 3 The antimicrobial activity of 4 were promising as the highest log reduction value was observed when compared to the porphyrin conjugates.
- Full Text:
- Date Issued: 2015
- Authors: Managa, Muthumuni Elizabeth
- Date: 2015
- Subjects: Photochemotherapy , Anti-infective agents , Porphyrins , Phthalocyanines , Platinum , Nanoparticles , Bioconjugates , Electrospinning
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4539 , http://hdl.handle.net/10962/d1017919
- Description: This work reports on the conjugation of differently shaped Pt nanoparticles (PtNPs) with ClGa(III) 5,10,15,20-tetrakis-(4-carboxyphenyl) porphyrin (1) as well as chloro - (5,10,15,20-tetrakis (4- (4- carboxy phenycarbonoimidoyl) phenyl) porphyrinato) gallium(III) (2) The work also reports on platination of dihydroxosilicon octacarboxyphthalocyanine (OH)₂SiOCPc (3) to give dihydroxosilicontris(diaquaplatinum)octacarboxyphthalocyanine (OH)₂SiOCPc(Pt)₃ (4). The resulting conjugates were used for photodynamic antimicrobial chemotherapy against S. aureus, E. coli and C. albicans. The degree of photo-inactivation is dependent on concentration of the conjugates, light dose (fluence) and illumination time. The log reduction obtained for 1 when conjugated to cubic PtNPs was 4.64 log (which indicate 99.99 percent of the bacteria have been killed), which is much higher than 3.94 log unit for 1-hexagonal PtNPs and 3.31 log units for 1-unshaped PtNPs. Complex 2 conjugated to hexagonal PtNPs showed 18 nm red shift in the Soret band when compared to 2 alone. Complex 2 and 2-hexagonal PtNPs as well showed promising photodynamic antimicrobial chemotherapy (PACT) activity against S. aureus, E. coli and C. albicans in solution where the log reduction obtained was 4.92, 3.76, and 3.95 respectively for 2-hexagonal PtNPs. The singlet oxygen quantum yields obtained were higher at 0.56 for 2-hexagonl PtNPs in DMF while that of 2 was 0.52 in the same solvent. This resulted in improved PACT activity for 2-hexagonal PtNPs compared to 2. Complex 4 showed slight blue shifting of the absorption spectrum when compared to complex 3 The antimicrobial activity of 4 were promising as the highest log reduction value was observed when compared to the porphyrin conjugates.
- Full Text:
- Date Issued: 2015
Photophysical studies of Zinc phthalocyanine-silica nanoparticles conjugates
- Authors: Fashina, Adedayo
- Date: 2015
- Subjects: Nanoparticles , Phthalocyanines , Zinc , Silica , Photochemistry , Adsorption
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4537 , http://hdl.handle.net/10962/d1017917
- Description: This thesis reports on the synthesis and characterization of both symmetrical and asymmetrical Zinc phthalocyanine complexes. The complexes contained groups such as carboxylic, amino and alkyne for covalent grafting to the surface of silica nanoparticles. The use of symmetrical and asymmetrical complexes was geared towards comparing the non-specific binding of the symmetrical complexes to the specific binding observed in the asymmetrical complexes. The complexes were also doped within the silica matrix and compared to the surface grafted conjugates. The complexes and the conjugates were well characterized with a variety of techniques. The fluorescence lifetimes of the phthalocyanine complexes containing either terminal carboxylic groups or an alkyne group showed a mono-exponential decay while the amino containing phthalocyanine complexes gave a bi-exponential decay. A similar trend was observed for their respective conjugates. Some of the conjugates of the asymmetrical complexes showed a decrease in fluorescence lifetimes and a corresponding decrease in fluorescence quantum yields. The fluorescence quantum yields for all the symmetrical complexes studied showed either an improvement or retained the luminescence of the grafted phthalocyanine complex. Most of the conjugates showed a faster intersystem crossing time in comparison to the complexes alone. The grafted or doped conjugates containing symmetrical phthalocyanine complexes with carboxyl groups showed improvements both in fluorescence and triplet quantum yields. All the conjugates except two showed an increase in triplet lifetimes when compared to their respective phthalocyanine complexes. Optical nonlinearities of nine of the phthalocyanine complexes were studied and all the complexes showed characteristic reverse saturable absorption behavior. Complex 10 showed the most promising optical limiting behavior. The aggregation and dissolution studies of the conjugates were also carried out in a simulated biological medium and the silicon level detected was noticed to have increased with incubation time.
- Full Text:
- Date Issued: 2015
- Authors: Fashina, Adedayo
- Date: 2015
- Subjects: Nanoparticles , Phthalocyanines , Zinc , Silica , Photochemistry , Adsorption
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4537 , http://hdl.handle.net/10962/d1017917
- Description: This thesis reports on the synthesis and characterization of both symmetrical and asymmetrical Zinc phthalocyanine complexes. The complexes contained groups such as carboxylic, amino and alkyne for covalent grafting to the surface of silica nanoparticles. The use of symmetrical and asymmetrical complexes was geared towards comparing the non-specific binding of the symmetrical complexes to the specific binding observed in the asymmetrical complexes. The complexes were also doped within the silica matrix and compared to the surface grafted conjugates. The complexes and the conjugates were well characterized with a variety of techniques. The fluorescence lifetimes of the phthalocyanine complexes containing either terminal carboxylic groups or an alkyne group showed a mono-exponential decay while the amino containing phthalocyanine complexes gave a bi-exponential decay. A similar trend was observed for their respective conjugates. Some of the conjugates of the asymmetrical complexes showed a decrease in fluorescence lifetimes and a corresponding decrease in fluorescence quantum yields. The fluorescence quantum yields for all the symmetrical complexes studied showed either an improvement or retained the luminescence of the grafted phthalocyanine complex. Most of the conjugates showed a faster intersystem crossing time in comparison to the complexes alone. The grafted or doped conjugates containing symmetrical phthalocyanine complexes with carboxyl groups showed improvements both in fluorescence and triplet quantum yields. All the conjugates except two showed an increase in triplet lifetimes when compared to their respective phthalocyanine complexes. Optical nonlinearities of nine of the phthalocyanine complexes were studied and all the complexes showed characteristic reverse saturable absorption behavior. Complex 10 showed the most promising optical limiting behavior. The aggregation and dissolution studies of the conjugates were also carried out in a simulated biological medium and the silicon level detected was noticed to have increased with incubation time.
- Full Text:
- Date Issued: 2015
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
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
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