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
Enumeration, conformation sampling and population of libraries of peptide macrocycles for the search of chemotherapeutic cardioprotection agents
- Authors: Sigauke, Lester Takunda
- Date: 2019
- Subjects: Peptides -- Synthesis , Macrocyclic compounds , Drug development , Drug discovery , Cardiovascular system -- Diseases -- Prevention , Proteins -- Synthesis
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/116056 , vital:34293
- Description: Peptides are uniquely endowed with features that allow them to perturb previously difficult to drug biomolecular targets. Peptide macrocycles in particular have seen a flurry of recent interest due to their enhanced bioavailability, tunability and specificity. Although these properties make them attractive hit-candidates in early stage drug discovery, knowing which peptides to pursue is non‐trivial due to the magnitude of the peptide sequence space. Computational screening approaches show promise in their ability to address the size of this search space but suffer from their inability to accurately interrogate the conformational landscape of peptide macrocycles. We developed an in‐silico compound enumerator that was tasked with populating a conformationally laden peptide virtual library. This library was then used in the search for cardio‐protective agents (that may be administered, reducing tissue damage during reperfusion after ischemia (heart attacks)). Our enumerator successfully generated a library of 15.2 billion compounds, requiring the use of compression algorithms, conformational sampling protocols and management of aggregated compute resources in the context of a local cluster. In the absence of experimental biophysical data, we performed biased sampling during alchemical molecular dynamics simulations in order to observe cyclophilin‐D perturbation by cyclosporine A and its mitochondrial targeted analogue. Reliable intermediate state averaging through a WHAM analysis of the biased dynamic pulling simulations confirmed that the cardio‐protective activity of cyclosporine A was due to its mitochondrial targeting. Paralleltempered solution molecular dynamics in combination with efficient clustering isolated the essential dynamics of a cyclic peptide scaffold. The rapid enumeration of skeletons from these essential dynamics gave rise to a conformation laden virtual library of all the 15.2 Billion unique cyclic peptides (given the limits on peptide sequence imposed). Analysis of this library showed the exact extent of physicochemical properties covered, relative to the bare scaffold precursor. Molecular docking of a subset of the virtual library against cyclophilin‐D showed significant improvements in affinity to the target (relative to cyclosporine A). The conformation laden virtual library, accessed by our methodology, provided derivatives that were able to make many interactions per peptide with the cyclophilin‐D target. Machine learning methods showed promise in the training of Support Vector Machines for synthetic feasibility prediction for this library. The synergy between enumeration and conformational sampling greatly improves the performance of this library during virtual screening, even when only a subset is used.
- Full Text:
- Date Issued: 2019
- Authors: Sigauke, Lester Takunda
- Date: 2019
- Subjects: Peptides -- Synthesis , Macrocyclic compounds , Drug development , Drug discovery , Cardiovascular system -- Diseases -- Prevention , Proteins -- Synthesis
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/116056 , vital:34293
- Description: Peptides are uniquely endowed with features that allow them to perturb previously difficult to drug biomolecular targets. Peptide macrocycles in particular have seen a flurry of recent interest due to their enhanced bioavailability, tunability and specificity. Although these properties make them attractive hit-candidates in early stage drug discovery, knowing which peptides to pursue is non‐trivial due to the magnitude of the peptide sequence space. Computational screening approaches show promise in their ability to address the size of this search space but suffer from their inability to accurately interrogate the conformational landscape of peptide macrocycles. We developed an in‐silico compound enumerator that was tasked with populating a conformationally laden peptide virtual library. This library was then used in the search for cardio‐protective agents (that may be administered, reducing tissue damage during reperfusion after ischemia (heart attacks)). Our enumerator successfully generated a library of 15.2 billion compounds, requiring the use of compression algorithms, conformational sampling protocols and management of aggregated compute resources in the context of a local cluster. In the absence of experimental biophysical data, we performed biased sampling during alchemical molecular dynamics simulations in order to observe cyclophilin‐D perturbation by cyclosporine A and its mitochondrial targeted analogue. Reliable intermediate state averaging through a WHAM analysis of the biased dynamic pulling simulations confirmed that the cardio‐protective activity of cyclosporine A was due to its mitochondrial targeting. Paralleltempered solution molecular dynamics in combination with efficient clustering isolated the essential dynamics of a cyclic peptide scaffold. The rapid enumeration of skeletons from these essential dynamics gave rise to a conformation laden virtual library of all the 15.2 Billion unique cyclic peptides (given the limits on peptide sequence imposed). Analysis of this library showed the exact extent of physicochemical properties covered, relative to the bare scaffold precursor. Molecular docking of a subset of the virtual library against cyclophilin‐D showed significant improvements in affinity to the target (relative to cyclosporine A). The conformation laden virtual library, accessed by our methodology, provided derivatives that were able to make many interactions per peptide with the cyclophilin‐D target. Machine learning methods showed promise in the training of Support Vector Machines for synthetic feasibility prediction for this library. The synergy between enumeration and conformational sampling greatly improves the performance of this library during virtual screening, even when only a subset is used.
- Full Text:
- Date Issued: 2019
Nonlinear optical responses of targeted phthalocyanines when conjugated with nanomaterials or fabricated into polymer thin films
- Authors: Nwaji, Njemuwa Njoku
- Date: 2019
- Subjects: Electrochemistry , Phthalocyanines , Nanoparticles , Bioconjugates , Thin films , Polymers , Nonlinear optics , Nonlinear optical spectroscopy , Nanostructured materials , Raman effect
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/71625 , vital:29926
- Description: A number of zinc, gallium and indium metallophthalocyanines (MPcs) with diverse substituents have been synthesized and characterized using various characterization tools such as proton nuclear magnetic resonance (1HNMR), matrix assisted laser desorption time of flight (MALDI-TOF) mass spectrometry, Fourier-transformed infra-red (FT-IR), Ultraviolet-visible (Uv-vis) spectrophotometry, magnetic circular dichroism and CHNS elemental analysis. The time dependent density functional theory was employed to probe the origin of spectroscopic information in these complexes. Complexes with gallium and indium as central metal showed higher triplet quantum yield compared to the zinc derivatives. Some of the MPcs were covalently linked to nanomaterials such as CdTe, CdTeSe, CdTeSe/ZnO, graphene quantum dots (GQDs) as well as metallic gold (AuNPs) and silver (AgNPs) nanoparticles. Others were either surface assembled onto AuNPs and AgNPs or embedded into polystyrene as polymer source. The phthalocyanine-nanomaterial composites (Pc-NMCs) were characterized with FT-IR, UV-visible spectrophotometry, transmission electron microscopy (TEM), dynamic light scattering (DLS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD). The thickness of the thin films was determined by utilization of the knife edge attachment of the A Bruker D8 Discover X-ray diffraction. The optical limiting properties (using the open-aperture Z-scan technique) of the MPcs and the Pc-NMCs were investigated. The investigated MPcs complexes generally showed good optical limiting properties. The nonlinear optical response of the MPcs were improved in the presence of nanomaterials such as the semiconductor quantum dots (SQDs), graphene quantum dots (GQDs) as well as metallic AuNPs and AgNPs with MPc-QDs showing the best optical limiting behavior. The optical limiting properties of the MPcs were greatly enhanced in the presence of polymer thin films.
- Full Text:
- Date Issued: 2019
- Authors: Nwaji, Njemuwa Njoku
- Date: 2019
- Subjects: Electrochemistry , Phthalocyanines , Nanoparticles , Bioconjugates , Thin films , Polymers , Nonlinear optics , Nonlinear optical spectroscopy , Nanostructured materials , Raman effect
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/71625 , vital:29926
- Description: A number of zinc, gallium and indium metallophthalocyanines (MPcs) with diverse substituents have been synthesized and characterized using various characterization tools such as proton nuclear magnetic resonance (1HNMR), matrix assisted laser desorption time of flight (MALDI-TOF) mass spectrometry, Fourier-transformed infra-red (FT-IR), Ultraviolet-visible (Uv-vis) spectrophotometry, magnetic circular dichroism and CHNS elemental analysis. The time dependent density functional theory was employed to probe the origin of spectroscopic information in these complexes. Complexes with gallium and indium as central metal showed higher triplet quantum yield compared to the zinc derivatives. Some of the MPcs were covalently linked to nanomaterials such as CdTe, CdTeSe, CdTeSe/ZnO, graphene quantum dots (GQDs) as well as metallic gold (AuNPs) and silver (AgNPs) nanoparticles. Others were either surface assembled onto AuNPs and AgNPs or embedded into polystyrene as polymer source. The phthalocyanine-nanomaterial composites (Pc-NMCs) were characterized with FT-IR, UV-visible spectrophotometry, transmission electron microscopy (TEM), dynamic light scattering (DLS), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD). The thickness of the thin films was determined by utilization of the knife edge attachment of the A Bruker D8 Discover X-ray diffraction. The optical limiting properties (using the open-aperture Z-scan technique) of the MPcs and the Pc-NMCs were investigated. The investigated MPcs complexes generally showed good optical limiting properties. The nonlinear optical response of the MPcs were improved in the presence of nanomaterials such as the semiconductor quantum dots (SQDs), graphene quantum dots (GQDs) as well as metallic AuNPs and AgNPs with MPc-QDs showing the best optical limiting behavior. The optical limiting properties of the MPcs were greatly enhanced in the presence of polymer thin films.
- Full Text:
- Date Issued: 2019
Ph-responsive liposomal systems for site-specific pulmonary delivery of anti-tubercular drugs
- Nkanga, Christian Isalomboto
- Authors: Nkanga, Christian Isalomboto
- Date: 2019
- Subjects: Tuberculosis -- Chemotherapy , Lipsomes , Drug carriers (Pharmacy) , Rifampin , Hydrogen-ion concentration , Hydrogen-ion concentration -- Physiological effect
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/125832 , vital:35822
- Description: Tuberculosis (TB) is an infectious disease that has been reported to be the ninth leading cause of death worldwide, even though mostly considered as a poverty related disease. Despite the existence of potent anti-tubercular drugs (ATBDs), such as rifampicin (RIF) and isoniazid (INH), TB remains the major killer among many microbial diseases over the last five years. Although several factors are to be blamed for this deadly status, the most crucial issues encompass both the self-defensiveness of the causative agent (Mycobacterium tuberculosis), including its intra-macrophage location that compromises ATBDs accessibility, and the widespread/off target distribution of ATBDs. The need for novel drug delivery strategies therefore arises to provide selective distribution of ATBDs at the infected site. Among the drug vehicles explored in this field, liposomes have been reported to be the most suitable drug carriers due to their rapid uptake by alveolar macrophages, where M. tuberculosis often resides. Since liposomes experience media of different pH throughout the cell uptake process (endocytosis/phagocytosis), the use of pH change as a stimulus for controlled release looks promising for enhancing intra-macrophage delivery and minimizing premature ‘off-target’ release of ATBDs. However, the costly status of liposome technology, due to the use of sophisticated procedures and expensive materials (especially for pH-dependent delivery, where special lipids are required), may preclude wider developments of liposomal products, especially for the developing world. This study aimed at investigating liposomal encapsulation of pH-sensitive and fluorescent hydrazone derivatives of INH using crude soybean lecithin, as a cost-effective option for site-specific delivery combined with potential bio-imaging features. Another objective was to explore encapsulation of INH hydrazone derivatives with and without RIF in liposomes using a simple and organic solvent-free preparation method. Initially, INH was coupled with 4-hydroxy-benzaldehyde to yield a conjugate (INH-HB) that was encapsulated in liposomes using film hydration method with acceptable encapsulation efficiency (î), about 89 %. The prepared INH-HB loaded liposomes (IHL) were characterized by means of dynamic light scattering (DLS), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The release of INH from IHL was evaluated over 12 hours in media of different pH using dialysis. As hypothesized, pH dependent release of INH from IHL was observed with 22, 69, 83 and 100 % release obtained in media of pH 7.4, 6.4, 5.4 and 4.4, respectively. From this experimental trial, further development was undertaken by conjugating INH to a hydrophobic fluorescent tag, zinc (II) phthalocyanine (PC), through hydrazone linkages. The obtained conjugate (PC-INH) was loaded into liposomes (PIL) that were characterized using various spectroscopic techniques, including UV-Vis absorption and energy dispersive X-ray spectroscopy, which suggested the presence of PC-INH within the lipid bilayers. The release study performed in different pH media revealed 22, 41, 97 and 100 % of INH, respectively released at pH 7.4, 6.4, 5.4 and 4.4. This confirmed the potential of pH-triggered drug release from liposomes loaded with hydrazone drug derivatives. In addition, successful encapsulation of PC-INH using crude soybean lecithin inspired a new opening towards development of multimodal liposomes that could achieve controlled drug release with added benefits of image-guided biological tracking. However, the hydrophobic nature of PC-INH requires an effective strategy that could improve its solubility and favour extensive development. In this context, the tetra-substituted structure of PC-INH brought up the hypothesis that cyclodextrin (CD) complexation would facilitate PC-INH encapsulation in liposomes using an organic solvent-free method, called here the “heating method” (HM). Inclusion complexes of PC-INH with various CDs were therefore investigated, with gamma-CD complex (CP) giving the best results. These complexes were prepared in both solution and solid-state and further comprehensively characterized using UV-Vis spectroscopy, magnetic circular dichroism, NMR spectroscopy, diffusion ordered spectroscopy, DSC, XRD and Fourier transform infrared spectroscopy. CP-loaded liposomes prepared using HM exhibited greater î than film hydration liposomes, about 70 % versus 56 %, respectively. The HM-liposomal system (CPL) exhibited potentially useful nano particulate characteristics (i.e. mean particle size 240 nm and Zeta potential –57 mV), which remained unchanged over 5 weeks of stability study at 4 °C, and pH-dependent INH release behaviour alike PIL. Furthermore, CP was co-encapsulated with rifampicin (RIF) in liposomes using HM to investigate the possibility for future combination therapy. 1H-NMR spectroscopy, DSC, XRD and photophysical studies were performed for molecular assessment of the cargo in CP-RIF co-loaded liposomes (CPRL). The mean particle size, Zeta potential and î of CPRL were respectively 594 nm, –50 mV, 58 % for CP and 86 % for RIF. CPRL exhibited much higher release rates for both INH and RIF at pH 6.4, compared to those tested at pH 7.4. In addition, there was no cytotoxicity on HeLa cells, but attractive lung fibroblasts and epithelial cells uptake and viability. Hence, CPRL are promising for targeted ATBD delivery to alveolar macrophages following pulmonary administration. Overall, the developed pH-responsive liposomal system holds the promise for new openings towards wider developments of multifunctional liposomes for site-specific controlled pulmonary delivery of antimicrobials drugs.
- Full Text:
- Date Issued: 2019
- Authors: Nkanga, Christian Isalomboto
- Date: 2019
- Subjects: Tuberculosis -- Chemotherapy , Lipsomes , Drug carriers (Pharmacy) , Rifampin , Hydrogen-ion concentration , Hydrogen-ion concentration -- Physiological effect
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/125832 , vital:35822
- Description: Tuberculosis (TB) is an infectious disease that has been reported to be the ninth leading cause of death worldwide, even though mostly considered as a poverty related disease. Despite the existence of potent anti-tubercular drugs (ATBDs), such as rifampicin (RIF) and isoniazid (INH), TB remains the major killer among many microbial diseases over the last five years. Although several factors are to be blamed for this deadly status, the most crucial issues encompass both the self-defensiveness of the causative agent (Mycobacterium tuberculosis), including its intra-macrophage location that compromises ATBDs accessibility, and the widespread/off target distribution of ATBDs. The need for novel drug delivery strategies therefore arises to provide selective distribution of ATBDs at the infected site. Among the drug vehicles explored in this field, liposomes have been reported to be the most suitable drug carriers due to their rapid uptake by alveolar macrophages, where M. tuberculosis often resides. Since liposomes experience media of different pH throughout the cell uptake process (endocytosis/phagocytosis), the use of pH change as a stimulus for controlled release looks promising for enhancing intra-macrophage delivery and minimizing premature ‘off-target’ release of ATBDs. However, the costly status of liposome technology, due to the use of sophisticated procedures and expensive materials (especially for pH-dependent delivery, where special lipids are required), may preclude wider developments of liposomal products, especially for the developing world. This study aimed at investigating liposomal encapsulation of pH-sensitive and fluorescent hydrazone derivatives of INH using crude soybean lecithin, as a cost-effective option for site-specific delivery combined with potential bio-imaging features. Another objective was to explore encapsulation of INH hydrazone derivatives with and without RIF in liposomes using a simple and organic solvent-free preparation method. Initially, INH was coupled with 4-hydroxy-benzaldehyde to yield a conjugate (INH-HB) that was encapsulated in liposomes using film hydration method with acceptable encapsulation efficiency (î), about 89 %. The prepared INH-HB loaded liposomes (IHL) were characterized by means of dynamic light scattering (DLS), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The release of INH from IHL was evaluated over 12 hours in media of different pH using dialysis. As hypothesized, pH dependent release of INH from IHL was observed with 22, 69, 83 and 100 % release obtained in media of pH 7.4, 6.4, 5.4 and 4.4, respectively. From this experimental trial, further development was undertaken by conjugating INH to a hydrophobic fluorescent tag, zinc (II) phthalocyanine (PC), through hydrazone linkages. The obtained conjugate (PC-INH) was loaded into liposomes (PIL) that were characterized using various spectroscopic techniques, including UV-Vis absorption and energy dispersive X-ray spectroscopy, which suggested the presence of PC-INH within the lipid bilayers. The release study performed in different pH media revealed 22, 41, 97 and 100 % of INH, respectively released at pH 7.4, 6.4, 5.4 and 4.4. This confirmed the potential of pH-triggered drug release from liposomes loaded with hydrazone drug derivatives. In addition, successful encapsulation of PC-INH using crude soybean lecithin inspired a new opening towards development of multimodal liposomes that could achieve controlled drug release with added benefits of image-guided biological tracking. However, the hydrophobic nature of PC-INH requires an effective strategy that could improve its solubility and favour extensive development. In this context, the tetra-substituted structure of PC-INH brought up the hypothesis that cyclodextrin (CD) complexation would facilitate PC-INH encapsulation in liposomes using an organic solvent-free method, called here the “heating method” (HM). Inclusion complexes of PC-INH with various CDs were therefore investigated, with gamma-CD complex (CP) giving the best results. These complexes were prepared in both solution and solid-state and further comprehensively characterized using UV-Vis spectroscopy, magnetic circular dichroism, NMR spectroscopy, diffusion ordered spectroscopy, DSC, XRD and Fourier transform infrared spectroscopy. CP-loaded liposomes prepared using HM exhibited greater î than film hydration liposomes, about 70 % versus 56 %, respectively. The HM-liposomal system (CPL) exhibited potentially useful nano particulate characteristics (i.e. mean particle size 240 nm and Zeta potential –57 mV), which remained unchanged over 5 weeks of stability study at 4 °C, and pH-dependent INH release behaviour alike PIL. Furthermore, CP was co-encapsulated with rifampicin (RIF) in liposomes using HM to investigate the possibility for future combination therapy. 1H-NMR spectroscopy, DSC, XRD and photophysical studies were performed for molecular assessment of the cargo in CP-RIF co-loaded liposomes (CPRL). The mean particle size, Zeta potential and î of CPRL were respectively 594 nm, –50 mV, 58 % for CP and 86 % for RIF. CPRL exhibited much higher release rates for both INH and RIF at pH 6.4, compared to those tested at pH 7.4. In addition, there was no cytotoxicity on HeLa cells, but attractive lung fibroblasts and epithelial cells uptake and viability. Hence, CPRL are promising for targeted ATBD delivery to alveolar macrophages following pulmonary administration. Overall, the developed pH-responsive liposomal system holds the promise for new openings towards wider developments of multifunctional liposomes for site-specific controlled pulmonary delivery of antimicrobials drugs.
- Full Text:
- Date Issued: 2019
Photocatalytic treatment of organic and inorganic water pollutants using zinc phthalocyanine-cobalt ferrite magnetic nanoparticle conjugates
- Authors: Mapukata, Sivuyisiwe
- Date: 2019
- Subjects: Phthalocyanines , Cobalt ferrite , Zinc , Nanoparticles
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67603 , vital:29119
- Description: This work explores the synthesis and photophysicochemical properties of zinc phthalocyanines when conjugated to cobalt ferrite magnetic nanoparticles. Phthalocyanines with amine and carboxylic acid functional groups were synthesised so as to covalently link them via amide bonds to cobalt ferrite magnetic nanoparticles with carboxylic acid and amine groups, respectively. Spectroscopic and microscopic studies confirmed the formation and purity of the phthalocyanine-cobalt ferrite magnetic nanoparticle conjugates which exhibited enhanced triplet and singlet quantum yields compared to the phthalocyanines alone. The studies showed that the presence of cobalt ferrite nanoparticles significantly lowered fluorescence quantum yields and lifetimes. The conjugates not only showed much higher singlet oxygen quantum yields compared to the phthalocyanines alone but were also attractive because of their magnetic regeneration and hence reusability properties, making them appealing for photocatalytic applications. The photocatalytic ability of some of the phthalocyanines and their conjugates were then tested based on their photooxidation and photoreduction abilities on Methyl Orange and hexavalent chromium, respectively. For catalyst support, some of the zinc phthalocyanines, cobalt ferrite magnetic nanoparticles and their respective conjugates were successfully incorporated into electrospun polystyrene and polyamide-6 fibers. Spectral characteristics of the functionalized electrospun fibers confirmed the incorporation of the photocatalysts and indicated that the phthalocyanines and their respective conjuagates remained intact with their integrity maintained within the polymeric fiber matrices. The photochemical properties of the complexes were equally maintained within the electrospun fibers hence they were applied in the photooxidation of azo dyes using Orange G and Methyl Orange as model organic compounds.
- Full Text:
- Date Issued: 2019
- Authors: Mapukata, Sivuyisiwe
- Date: 2019
- Subjects: Phthalocyanines , Cobalt ferrite , Zinc , Nanoparticles
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67603 , vital:29119
- Description: This work explores the synthesis and photophysicochemical properties of zinc phthalocyanines when conjugated to cobalt ferrite magnetic nanoparticles. Phthalocyanines with amine and carboxylic acid functional groups were synthesised so as to covalently link them via amide bonds to cobalt ferrite magnetic nanoparticles with carboxylic acid and amine groups, respectively. Spectroscopic and microscopic studies confirmed the formation and purity of the phthalocyanine-cobalt ferrite magnetic nanoparticle conjugates which exhibited enhanced triplet and singlet quantum yields compared to the phthalocyanines alone. The studies showed that the presence of cobalt ferrite nanoparticles significantly lowered fluorescence quantum yields and lifetimes. The conjugates not only showed much higher singlet oxygen quantum yields compared to the phthalocyanines alone but were also attractive because of their magnetic regeneration and hence reusability properties, making them appealing for photocatalytic applications. The photocatalytic ability of some of the phthalocyanines and their conjugates were then tested based on their photooxidation and photoreduction abilities on Methyl Orange and hexavalent chromium, respectively. For catalyst support, some of the zinc phthalocyanines, cobalt ferrite magnetic nanoparticles and their respective conjugates were successfully incorporated into electrospun polystyrene and polyamide-6 fibers. Spectral characteristics of the functionalized electrospun fibers confirmed the incorporation of the photocatalysts and indicated that the phthalocyanines and their respective conjuagates remained intact with their integrity maintained within the polymeric fiber matrices. The photochemical properties of the complexes were equally maintained within the electrospun fibers hence they were applied in the photooxidation of azo dyes using Orange G and Methyl Orange as model organic compounds.
- Full Text:
- Date Issued: 2019
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
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
Physicochemical properties and photodynamic therapy activities of indium and zinc phthalocyanine-nanoparticle conjugates
- Authors: Dube, Edith
- Date: 2019
- Subjects: Indium , Zinc , Phthalocyanines , Breast -- Cancer -- Photochemotherapy , Nanoparticles
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/76506 , vital:30589
- Description: The syntheses and characterization of symmetric and asymmetric Pcs functionalized at the peripheral position are reported. The Pcs contain either zinc or indium as central metals and have carboxyphenoxy, phenoxy propanoic acid, benzothiazole phenoxy, thiophine ethoxy or di-O-isopropylidene-α-D-glucopyranose as ring substituents. The Pcs were linked to NPs via an amide bond or through self-assembly. The photophysics and photochemistry of the Pcs were assessed when alone and with conjugates. All the studied Pcs showed good photophysicochemical behaviour with relatively high triplet and singlet oxygen quantum yields corresponding to their low fluorescence quantum yield. The Pcs with indium in their central cavity exhibited higher triplet and singlet oxygen quantum yields in comparison to their zinc counterparts due to the heavy–atom effect obtained from the former. Asymmetrical Pcs displayed higher triplet and singlet oxygen quantum yields than their symmetrical counterparts. The triplet quantum yield, generally increased on linkage to nanoparticles (NPs) due to the heavy–atom effect of gold and silver in NPs. The conjugates to gold nanospheres yielded higher triplet and singlet quantum yields than their gold nanotriangles counterparts due to the higher loading by the former probably encouraged by their relatively small particle size. The in vitro dark cytotoxicity and photodynamic therapy of selected Pc complexes and conjugates against MCF-7 cells was tested. All studied Pc complexes and conjugates showed minimum dark toxicity making them applicable for PDT. All complexes displayed poor phototoxicity with >50Îll viability at concentrations≤ 160μg/mL, however the conjugates showed<50% cell viabilityatconcentrations≤ 160μg/mLprobably due to the enhanced singlet oxygen quantum yield. The findings from this work show the importance of linking photosensitises such as phthalocyanines to metal nanoparticles for the enhancement ofsinglet oxygen quantum yield and ultimately the photodynamic effect.
- Full Text:
- Date Issued: 2019
- Authors: Dube, Edith
- Date: 2019
- Subjects: Indium , Zinc , Phthalocyanines , Breast -- Cancer -- Photochemotherapy , Nanoparticles
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/76506 , vital:30589
- Description: The syntheses and characterization of symmetric and asymmetric Pcs functionalized at the peripheral position are reported. The Pcs contain either zinc or indium as central metals and have carboxyphenoxy, phenoxy propanoic acid, benzothiazole phenoxy, thiophine ethoxy or di-O-isopropylidene-α-D-glucopyranose as ring substituents. The Pcs were linked to NPs via an amide bond or through self-assembly. The photophysics and photochemistry of the Pcs were assessed when alone and with conjugates. All the studied Pcs showed good photophysicochemical behaviour with relatively high triplet and singlet oxygen quantum yields corresponding to their low fluorescence quantum yield. The Pcs with indium in their central cavity exhibited higher triplet and singlet oxygen quantum yields in comparison to their zinc counterparts due to the heavy–atom effect obtained from the former. Asymmetrical Pcs displayed higher triplet and singlet oxygen quantum yields than their symmetrical counterparts. The triplet quantum yield, generally increased on linkage to nanoparticles (NPs) due to the heavy–atom effect of gold and silver in NPs. The conjugates to gold nanospheres yielded higher triplet and singlet quantum yields than their gold nanotriangles counterparts due to the higher loading by the former probably encouraged by their relatively small particle size. The in vitro dark cytotoxicity and photodynamic therapy of selected Pc complexes and conjugates against MCF-7 cells was tested. All studied Pc complexes and conjugates showed minimum dark toxicity making them applicable for PDT. All complexes displayed poor phototoxicity with >50Îll viability at concentrations≤ 160μg/mL, however the conjugates showed<50% cell viabilityatconcentrations≤ 160μg/mLprobably due to the enhanced singlet oxygen quantum yield. The findings from this work show the importance of linking photosensitises such as phthalocyanines to metal nanoparticles for the enhancement ofsinglet oxygen quantum yield and ultimately the photodynamic effect.
- Full Text:
- Date Issued: 2019
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
Syntheses and photophysico-chemical properties of phthalocyanines in the presence of silica nanoparticles
- Authors: Peteni, Siwaphiwe
- Date: 2019
- Subjects: Phthalocyanines , Silica , Nanoparticles , Bioconjugates
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67592 , vital:29118
- Description: This thesis reports on the syntheses and characterizationof symmetrical (charged and neutral), asymmetrical (neutral) metallophthalocyanines (MPcs) and subphthalocyanines (SubPcs). The charged and neutral Pcs were physically doped onto silica nanoparticles (SiNPs). The asymmetrical MPc was also chemically linked to SiNPs. Spectroscopic and microscopic techniques were used to confirm the formation of SiNPs-MPc conjugates. The photophysics and photochemistry of the MPcs were assessed when alone and in conjugates (with SiNPs). The studies showed no significant changes in fluorescence quantum yields (ϕF) and fluorescence lifetimes (ϕF) of MPcs following doping except for 2-SiNPs (2 = Zn tetraaminophenoxyphthalocyanines) and 6-SiNPs (doped) (6 = Zn tris[(4-(pyridine-4-ylthio)2-thio-4-methylthiazol-5yl) acetic acid phthalocyanine) where there was a decrease in the ϕF value. Also for 1-SiNPs (1 = unsubstituted ZnPc) there was an elongation in τF which could be due to the protection offered by SiNPs. Both charged/neutral MPcs displayed high triplet quantum yields (ϕT) and singlet quantum yields (ϕΔ) following doping except for 2-SiNPs where there was a decrease in the latter. For 1-SiNPs there was an increase in ϕT but a decrease inϕΔ .There wasa decrease in ϕT and an increase in ϕΔfor4-SiNPs (4 = Zn tetrasulfophenoxyphthalocyanine), the decrease in ϕT could be due to the orientation of theMPc in SiNPs. An increase in both ϕT and ϕΔ for 6-SiNPs (linked) compared to 6-SiNPs (doped) was observed. Complex 5 (5 = Zn tetra-kis-(dodecylmercapto) phthalocyanine) showed a low ϕΔ value.
- Full Text:
- Date Issued: 2019
- Authors: Peteni, Siwaphiwe
- Date: 2019
- Subjects: Phthalocyanines , Silica , Nanoparticles , Bioconjugates
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/67592 , vital:29118
- Description: This thesis reports on the syntheses and characterizationof symmetrical (charged and neutral), asymmetrical (neutral) metallophthalocyanines (MPcs) and subphthalocyanines (SubPcs). The charged and neutral Pcs were physically doped onto silica nanoparticles (SiNPs). The asymmetrical MPc was also chemically linked to SiNPs. Spectroscopic and microscopic techniques were used to confirm the formation of SiNPs-MPc conjugates. The photophysics and photochemistry of the MPcs were assessed when alone and in conjugates (with SiNPs). The studies showed no significant changes in fluorescence quantum yields (ϕF) and fluorescence lifetimes (ϕF) of MPcs following doping except for 2-SiNPs (2 = Zn tetraaminophenoxyphthalocyanines) and 6-SiNPs (doped) (6 = Zn tris[(4-(pyridine-4-ylthio)2-thio-4-methylthiazol-5yl) acetic acid phthalocyanine) where there was a decrease in the ϕF value. Also for 1-SiNPs (1 = unsubstituted ZnPc) there was an elongation in τF which could be due to the protection offered by SiNPs. Both charged/neutral MPcs displayed high triplet quantum yields (ϕT) and singlet quantum yields (ϕΔ) following doping except for 2-SiNPs where there was a decrease in the latter. For 1-SiNPs there was an increase in ϕT but a decrease inϕΔ .There wasa decrease in ϕT and an increase in ϕΔfor4-SiNPs (4 = Zn tetrasulfophenoxyphthalocyanine), the decrease in ϕT could be due to the orientation of theMPc in SiNPs. An increase in both ϕT and ϕΔ for 6-SiNPs (linked) compared to 6-SiNPs (doped) was observed. Complex 5 (5 = Zn tetra-kis-(dodecylmercapto) phthalocyanine) showed a low ϕΔ value.
- Full Text:
- Date Issued: 2019
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
Synthesis of pH responsive carriers for pulmonary drug delivery of anti-tuberculosis therapeutics: mesoporous silica nanoparticles and gelatin nanoparticles
- Authors: Ngoepe, Mpho Phehello
- Date: 2019
- Subjects: Drug delivery systems , Pulmonary pharmacology , Nanosilicon , Nanomedicine , Nanoparticles , Mesoporous materials , Silica , Tuberculosis -- Treatment
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/76519 , vital:30590
- Description: Pulmonary drug delivery has historically been used as a route for delivery of therapeutics for respiratory disease management. However, while there are many advantages, there are also some serious limitations, arising mostly from the physical aspects of the inhaler devices. This is more profound when the devices are the driving force for controlling particle size generation, which results in non-uniform particles that end up being swallowed/wasted/expelled. One promising solution to overcome this limitation is to pre-formulate nano/microscale particles with a high degree of manufacturing control. Nanomedicine has advanced such that there are already several nanoparticle formulations commercially available. In the case of tuberculosis treatment, there is an opportunity not only to examine the use of nanoparticles for inhalation therapy, but to take advantage of the fact that the physiochemical environment of diseased tissue is significantly different to health lung tissue (lower pH and increased enzyme concentrations). We formulated two series of nanoparticles, whose design included moieties that could respond to pH and enzymes. To address variability, a Box-Behnken statistical approach was followed to construct mesoporous silica nanoparticles. These “hard nanoparticles” can entrap both lipophilic and hydrophilic drugs and were coated with a pH-sensitive hydrazone linker. It was observed that pH, calcination temperature and ratio of water to silica source played the greatest role, not only in controlling the physicochemical properties of the nanoparticles but also the drug release rate. A second series of nanoparticles were synthesized based on gelatin. This was done partly to add support the comparison of hard (inorganic silica) versus soft, organic particles, but also to enable enzymatic degradation and drug release. Again, diseased lung tissue expresses increased concentrations of gelatinase enzymes that could be used to stimulate drug release at the site of the disease. In addition, it was observed that the non-ionic surfactant C12E10 could interact with the protein via hydrophobic interactions thus affecting the gelatin folding. The folding states affected crosslinking with the pH responsive linker, which in turn affected the rate of drug release. To support the synthetic work, we sought to develop a unique 3D lung model directly from MRI data of tuberculosis infected lungs. This would not only permit the evaluation of our nanoparticles but could be used as a proxy for in-vivo studies in future to predict lung deposition in diseased lung. Thus, this study shows that it is possible to synthesize pH and enzyme sensitive nanoparticles for pulmonary drug delivery in the treatment and management of pulmonary tuberculosis. These particles could be loaded with either hydrophobic or hydrophilic drugs and their distribution in the airway modelled using an in-silico 3D model based on real data. Further development and verification of these results should improve treatment for pulmonary diseases and conditions such as tuberculosis. This is especially urgent in the face of multi-drug resistance and poor side effects profiles for current treatment.
- Full Text:
- Date Issued: 2019
- Authors: Ngoepe, Mpho Phehello
- Date: 2019
- Subjects: Drug delivery systems , Pulmonary pharmacology , Nanosilicon , Nanomedicine , Nanoparticles , Mesoporous materials , Silica , Tuberculosis -- Treatment
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/76519 , vital:30590
- Description: Pulmonary drug delivery has historically been used as a route for delivery of therapeutics for respiratory disease management. However, while there are many advantages, there are also some serious limitations, arising mostly from the physical aspects of the inhaler devices. This is more profound when the devices are the driving force for controlling particle size generation, which results in non-uniform particles that end up being swallowed/wasted/expelled. One promising solution to overcome this limitation is to pre-formulate nano/microscale particles with a high degree of manufacturing control. Nanomedicine has advanced such that there are already several nanoparticle formulations commercially available. In the case of tuberculosis treatment, there is an opportunity not only to examine the use of nanoparticles for inhalation therapy, but to take advantage of the fact that the physiochemical environment of diseased tissue is significantly different to health lung tissue (lower pH and increased enzyme concentrations). We formulated two series of nanoparticles, whose design included moieties that could respond to pH and enzymes. To address variability, a Box-Behnken statistical approach was followed to construct mesoporous silica nanoparticles. These “hard nanoparticles” can entrap both lipophilic and hydrophilic drugs and were coated with a pH-sensitive hydrazone linker. It was observed that pH, calcination temperature and ratio of water to silica source played the greatest role, not only in controlling the physicochemical properties of the nanoparticles but also the drug release rate. A second series of nanoparticles were synthesized based on gelatin. This was done partly to add support the comparison of hard (inorganic silica) versus soft, organic particles, but also to enable enzymatic degradation and drug release. Again, diseased lung tissue expresses increased concentrations of gelatinase enzymes that could be used to stimulate drug release at the site of the disease. In addition, it was observed that the non-ionic surfactant C12E10 could interact with the protein via hydrophobic interactions thus affecting the gelatin folding. The folding states affected crosslinking with the pH responsive linker, which in turn affected the rate of drug release. To support the synthetic work, we sought to develop a unique 3D lung model directly from MRI data of tuberculosis infected lungs. This would not only permit the evaluation of our nanoparticles but could be used as a proxy for in-vivo studies in future to predict lung deposition in diseased lung. Thus, this study shows that it is possible to synthesize pH and enzyme sensitive nanoparticles for pulmonary drug delivery in the treatment and management of pulmonary tuberculosis. These particles could be loaded with either hydrophobic or hydrophilic drugs and their distribution in the airway modelled using an in-silico 3D model based on real data. Further development and verification of these results should improve treatment for pulmonary diseases and conditions such as tuberculosis. This is especially urgent in the face of multi-drug resistance and poor side effects profiles for current treatment.
- Full Text:
- Date Issued: 2019
Synthesis, characterisation and biological evaluation of novel anti-infective compounds bearing ferrocene, arylpyrrole, thiazolidinedione, quinoline and triazole moieties
- Authors: Oderinlo, Ogunyemi Olajide
- Date: 2019
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/114714 , vital:34016 , 10.21504/10962/114714
- Description: Expected release date-April 2022
- Full Text: false
- Date Issued: 2019
- Authors: Oderinlo, Ogunyemi Olajide
- Date: 2019
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/114714 , vital:34016 , 10.21504/10962/114714
- Description: Expected release date-April 2022
- Full Text: false
- Date Issued: 2019
Synthesis, characterisation and spectroscopic studies of diazine-N-oxide complexes of iron(II) towards the development of sensors
- Authors: Mpiti, Unako Bongani
- Date: 2019
- Subjects: Diazines , Ligands , Iron
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/94753 , vital:31075
- Description: The characteristic magnetic and spectroscopic features associated with the red monomeric or dimeric, and polymeric pyrazine-N-oxide (PyzNO) iron(II) perchlorate complexes; Fen(μ1,1-pyzNO)2n-2(pyzNO)3n+2(ClO4)2n (n = {1, 2}*, and the novel compound {Fe(μ-pyzNO-κN,κO)n-1(pyzNO-κN)2(pyzNO-κO)2}n(ClO4)2n†, respectively, were investigated. These properties are altered substantially when the complexes are hydrated; for instance, by atmospheric exposure. The resulting species; Fe(pyzNO)5(H2O)3(ClO4)2* and [Fe(pyzNO-κN)4(H2O)2](ClO4)2.2H2O†, which have different hues of a bright yellow colour, were found to exhibit strong paramagnetism, in contrast to their anhydrous precursors, which are ‘EPR silent’. A low spin → high spin crossover (LS→HS, SCO) transition was therefore proposed to occur as the complexes become hydrated by atmospheric moisture. The red→yellow colour change is reversible, and dehydration of the yellow species by heating regenerates the red variant, a feature which lends itself to the potential applicability of the system as a sensor. Further emphasis on this potential derives from the fact that the hydration/dehydration process, and its accompanying physical changes, appears reversible even after many such treatments. It became of interest, then, to determine if these changes were limited to water-exposed samples, or if they occurred under more diverse solvent atmospheres. The reversibility of such exposure on the structure of the novel polynuclear complex was therefore investigated. In general, it was found that there occurred a strong solvent-complex association for the more polar solvents. Red→yellow, LS→HS events were seen when the complex was exposed to the vapours of p-dioxane, acetaldehyde and formaldehyde, and to a lesser extent, to that of methanol. In each case, significant structural changes were seen, as evidenced be comparative XRPD and thermo-analytical studies. Some of these changes have however been ascribed to the effects of partial dissolution upon extended exposure of the complex to the associated media. Exposure to less polar solvent atmospheres, such as those of cyclohexane, toluene, diethyl ether, etc., showed some signs of mild solvent surface adhesion, but were unaccompanied by discernible magnetic and colour changes. Another novel complex was produced during attempts to synthesize the PyzNO complexes from a mixture of a 2,2’-dimethoxypropane (DMP) and ethanol (1:1, v/v), rather than the methanol/DMP mixture which had been alternately used. The formula of the resulting complex is Fe(pyzNO)6(ClO4)2.3EtOH*. This EPR inactive product was orange in colour, and transformed into a bright yellow, strongly paramagnetic species upon atmospheric exposure. Further solvent studies showed that this species interacted significantly with all solvents tested, but generally more strongly with increasing solvent polarity. Orange→yellow colour changes occurred in environments saturated with p-dioxane, acetaldehyde and formaldehyde vapours. The DMSO-exposed sample transformed to dark red, due to suspected PyzNO substitution by the solvent. The red→yellow and orange→yellow colour changes were ascribed to the formal substitution of O-coordinated PyzNO (μ-PyzNO in the polymeric complex) by the incoming solvent. The resulting structural and geometric changes stimulated a redistribution of d electrons among the new constituent molecular orbitals of altered energy and symmetry. Therefore, although the colour changes were not conventionally solvatochromic - in that the original structure was lost on exposure – data suggested that it was the coordination of species of higher donor strength that produced the observed bathochromic shifts. A novel 4,4’-bipyridine-N-oxide Fe(II) perchlorate complex, Fe2(bipyNO)5(ClO4)4.6MeOH†, was also produced, primarily for physicochemical comparison with the PyzNO complexes. No colour or magnetic changes were seen on atmospheric exposure. The original complex was observed to be inherently paramagnetic, and no SCO events occurred upon solvent exposure. Despite this, thermal analyses showed that the complex did exhibit the strong uptake of polar solvents in general, but particularly with acetaldehyde. Significant structural changes upon exposure were limited to surface phenomena, with the exception of the acetaldehyde-exposed sample.
- Full Text:
- Date Issued: 2019
- Authors: Mpiti, Unako Bongani
- Date: 2019
- Subjects: Diazines , Ligands , Iron
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/94753 , vital:31075
- Description: The characteristic magnetic and spectroscopic features associated with the red monomeric or dimeric, and polymeric pyrazine-N-oxide (PyzNO) iron(II) perchlorate complexes; Fen(μ1,1-pyzNO)2n-2(pyzNO)3n+2(ClO4)2n (n = {1, 2}*, and the novel compound {Fe(μ-pyzNO-κN,κO)n-1(pyzNO-κN)2(pyzNO-κO)2}n(ClO4)2n†, respectively, were investigated. These properties are altered substantially when the complexes are hydrated; for instance, by atmospheric exposure. The resulting species; Fe(pyzNO)5(H2O)3(ClO4)2* and [Fe(pyzNO-κN)4(H2O)2](ClO4)2.2H2O†, which have different hues of a bright yellow colour, were found to exhibit strong paramagnetism, in contrast to their anhydrous precursors, which are ‘EPR silent’. A low spin → high spin crossover (LS→HS, SCO) transition was therefore proposed to occur as the complexes become hydrated by atmospheric moisture. The red→yellow colour change is reversible, and dehydration of the yellow species by heating regenerates the red variant, a feature which lends itself to the potential applicability of the system as a sensor. Further emphasis on this potential derives from the fact that the hydration/dehydration process, and its accompanying physical changes, appears reversible even after many such treatments. It became of interest, then, to determine if these changes were limited to water-exposed samples, or if they occurred under more diverse solvent atmospheres. The reversibility of such exposure on the structure of the novel polynuclear complex was therefore investigated. In general, it was found that there occurred a strong solvent-complex association for the more polar solvents. Red→yellow, LS→HS events were seen when the complex was exposed to the vapours of p-dioxane, acetaldehyde and formaldehyde, and to a lesser extent, to that of methanol. In each case, significant structural changes were seen, as evidenced be comparative XRPD and thermo-analytical studies. Some of these changes have however been ascribed to the effects of partial dissolution upon extended exposure of the complex to the associated media. Exposure to less polar solvent atmospheres, such as those of cyclohexane, toluene, diethyl ether, etc., showed some signs of mild solvent surface adhesion, but were unaccompanied by discernible magnetic and colour changes. Another novel complex was produced during attempts to synthesize the PyzNO complexes from a mixture of a 2,2’-dimethoxypropane (DMP) and ethanol (1:1, v/v), rather than the methanol/DMP mixture which had been alternately used. The formula of the resulting complex is Fe(pyzNO)6(ClO4)2.3EtOH*. This EPR inactive product was orange in colour, and transformed into a bright yellow, strongly paramagnetic species upon atmospheric exposure. Further solvent studies showed that this species interacted significantly with all solvents tested, but generally more strongly with increasing solvent polarity. Orange→yellow colour changes occurred in environments saturated with p-dioxane, acetaldehyde and formaldehyde vapours. The DMSO-exposed sample transformed to dark red, due to suspected PyzNO substitution by the solvent. The red→yellow and orange→yellow colour changes were ascribed to the formal substitution of O-coordinated PyzNO (μ-PyzNO in the polymeric complex) by the incoming solvent. The resulting structural and geometric changes stimulated a redistribution of d electrons among the new constituent molecular orbitals of altered energy and symmetry. Therefore, although the colour changes were not conventionally solvatochromic - in that the original structure was lost on exposure – data suggested that it was the coordination of species of higher donor strength that produced the observed bathochromic shifts. A novel 4,4’-bipyridine-N-oxide Fe(II) perchlorate complex, Fe2(bipyNO)5(ClO4)4.6MeOH†, was also produced, primarily for physicochemical comparison with the PyzNO complexes. No colour or magnetic changes were seen on atmospheric exposure. The original complex was observed to be inherently paramagnetic, and no SCO events occurred upon solvent exposure. Despite this, thermal analyses showed that the complex did exhibit the strong uptake of polar solvents in general, but particularly with acetaldehyde. Significant structural changes upon exposure were limited to surface phenomena, with the exception of the acetaldehyde-exposed sample.
- Full Text:
- Date Issued: 2019
The preparation of BODIPY and porphyrin dyes and their cyclodextrin inclusion complexes and Pluronic® F-127 encapsulation micelles for use in PDT and PACT
- Authors: Molupe, Nthabeleng
- Date: 2019
- Subjects: Dyes and dyeing -- Chemistry , Drug delivery systems , Fluorescence spectroscopy , Cancer -- Photochemotherapy , Photosensitizing compounds -- Therapeutic use , Cyclodextrins -- Biotechnology , Nanoparticles
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/117574 , vital:34528
- Description: Several novel BODIPY dyes ((4,4′-difluoro-1,7-tetramethyl-3,5-(3-dithiophene)-2,6-diiodo-8-(4-dimethylamino)-4-bora-3a,4a-diaza-s-indacene (1c), 4,4′-difluoro-1,7-tetramethyl-3,5-(3 dithiophene)-2,6-diiodo-8-(4-methylthio)-4-bora-3a,4a-diaza-s-indacene (3c) and 4,4′-difluoro-1,7-tetramethyl-3,5-(4-dibenzyloxybenzene)-2,6-diiodo-8-(4-methylbenzoate)-4 bora-3a,4a-diaza-s-indacene (4c)) and porphyrins (tetraacenaphthylporphyrin (7a) and Sn(IV) tetraacenaphthylporphyrin (7b)) were synthesized and characterized. Previously reported BODIPY dyes (4,4′-difluoro-1,7-tetramethyl-3,5-(2-dihydroxy)-2,6-diiodo-8-(4-bromo)-4-bora-3a,4a-diaza-s-indacene (5) and 4,4′-difluoro-1,7-tetramethyl-3,5-(2-dithiophene)-2,6-diiodo-8-(phenyl)-4-bora-3a,4a-diaza-s-indacene (6)) were also used. Pluronic® F-127 and cyclodextrins were used as solubilizing drug delivery agents for the synthesized BODIPY dyes. The encapsulation of BODIPY dyes with Pluronic® F-127 micelles improved the water solubility of the BODIPY 5. Further modification of Pluronic® F-127 by coating with folate-functionalized chitosan for targeted delivery of BODIPY 1c and 6 was explored. The BODIPY dyes and their encapsulation complexes exhibited significant inhibition of human MCF-7 breast cancer cell growth. When cyclodextrins were used as nanocarriers, the inclusion complexes of BODIPY 4c with mβCD were found to enhance the water-solubility of the dye. Greater photoinactivation of Staphylococcus aureus was observed for the inclusion complexes when compared to the effect of solutions of non-complexed BODIPY 4c. The cyclodextrin inclusion complexes of porphyrin 7b with mβCD were also found to enhance the water-solubility of 7b. When the photodynamic effect was evaluated, solutions of the porphyrin alone and their inclusion complexes were found to have significant photodynamic effects against human MCF-7 breast cancer cells.
- Full Text:
- Date Issued: 2019
- Authors: Molupe, Nthabeleng
- Date: 2019
- Subjects: Dyes and dyeing -- Chemistry , Drug delivery systems , Fluorescence spectroscopy , Cancer -- Photochemotherapy , Photosensitizing compounds -- Therapeutic use , Cyclodextrins -- Biotechnology , Nanoparticles
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/117574 , vital:34528
- Description: Several novel BODIPY dyes ((4,4′-difluoro-1,7-tetramethyl-3,5-(3-dithiophene)-2,6-diiodo-8-(4-dimethylamino)-4-bora-3a,4a-diaza-s-indacene (1c), 4,4′-difluoro-1,7-tetramethyl-3,5-(3 dithiophene)-2,6-diiodo-8-(4-methylthio)-4-bora-3a,4a-diaza-s-indacene (3c) and 4,4′-difluoro-1,7-tetramethyl-3,5-(4-dibenzyloxybenzene)-2,6-diiodo-8-(4-methylbenzoate)-4 bora-3a,4a-diaza-s-indacene (4c)) and porphyrins (tetraacenaphthylporphyrin (7a) and Sn(IV) tetraacenaphthylporphyrin (7b)) were synthesized and characterized. Previously reported BODIPY dyes (4,4′-difluoro-1,7-tetramethyl-3,5-(2-dihydroxy)-2,6-diiodo-8-(4-bromo)-4-bora-3a,4a-diaza-s-indacene (5) and 4,4′-difluoro-1,7-tetramethyl-3,5-(2-dithiophene)-2,6-diiodo-8-(phenyl)-4-bora-3a,4a-diaza-s-indacene (6)) were also used. Pluronic® F-127 and cyclodextrins were used as solubilizing drug delivery agents for the synthesized BODIPY dyes. The encapsulation of BODIPY dyes with Pluronic® F-127 micelles improved the water solubility of the BODIPY 5. Further modification of Pluronic® F-127 by coating with folate-functionalized chitosan for targeted delivery of BODIPY 1c and 6 was explored. The BODIPY dyes and their encapsulation complexes exhibited significant inhibition of human MCF-7 breast cancer cell growth. When cyclodextrins were used as nanocarriers, the inclusion complexes of BODIPY 4c with mβCD were found to enhance the water-solubility of the dye. Greater photoinactivation of Staphylococcus aureus was observed for the inclusion complexes when compared to the effect of solutions of non-complexed BODIPY 4c. The cyclodextrin inclusion complexes of porphyrin 7b with mβCD were also found to enhance the water-solubility of 7b. When the photodynamic effect was evaluated, solutions of the porphyrin alone and their inclusion complexes were found to have significant photodynamic effects against human MCF-7 breast cancer cells.
- Full Text:
- Date Issued: 2019
BODIPY dyes for singlet oxygen and optical limiting applications
- Authors: Harris, Jessica
- Date: 2018
- Subjects: Photosensitizing compounds , Active oxygen -- Physiological effect , Photochemotherapy , Cancer -- Treatment , Nonlinear optics , BODIPY (Boron-dipyrromethene)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/58002 , vital:27014
- Description: A series of structurally related BODIPY dyes were synthesised and characterised. Their photophysical properties were studied in order to determine whether they would be suitable candidates for use as photosensitisers in the photodynamic therapy (PDT) treatment of cancer. The synthesis of two highly fluorescent BODIPY cores was achieved via the acid-catalysed condensation of a pyrrole and a functionalised aldehyde. In order to promote intersystem crossing, and hence improve the singlet oxygen generation of these dyes, bromine atoms were added at the 2,6-positions of the BODIPY core. These dibrominated analogues showed good singlet oxygen quantum yields, and excellent photostability in ethanol. In order to red-shift the main spectral bands of the BODIPY dyes towards the therapeutic window, vinyl/ styryl groups were introduced at the 3-, 5-, and 7-positions via a modified Knoevengal condensation reaction. The addition of vinyl/ styryl groups to the BODIPY core caused an increase in fluorescence quantum yield as well as a decrease in singlet oxygen quantum yield with respect to the dibrominated analogues. However, two of the red-shifted BODIPY dyes still showed moderate singlet oxygen quantum yields. The use of BODIPY dyes in nonlinear optics (NLO) was explored. The nonlinear optical characterisations and optical limiting properties of a series of 3,5-dithienylenevinylene BODIPY dyes were studied, both in dimethylformamide (DMF) solution and when embedded in poly(bisphenol A carbonate) (PBC) as thin films. The 3,5-dithienylenevinylene BODIPY dyes showed typical nonlinear absorption behaviour, with reverse saturable absorption (RSA) profiles, indicating that they have potential as optical limiters. The second-order hyperpolarizability (Y), and third-order nonlinear susceptibility (/m[/(3)]) values are also reported for these dyes. The optical limiting values of one of the BODIPY dyes in solution, and two of the BODIPY-embedded PBC films, were below the maximum threshold of 0.95 J-cm-2. The effect of addition of substituents on the electronic structure of the BODIPY dyes was investigated using TD-DFT calculations. The calculated trends closely followed those determined experimentally.
- Full Text:
- Date Issued: 2018
- Authors: Harris, Jessica
- Date: 2018
- Subjects: Photosensitizing compounds , Active oxygen -- Physiological effect , Photochemotherapy , Cancer -- Treatment , Nonlinear optics , BODIPY (Boron-dipyrromethene)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/58002 , vital:27014
- Description: A series of structurally related BODIPY dyes were synthesised and characterised. Their photophysical properties were studied in order to determine whether they would be suitable candidates for use as photosensitisers in the photodynamic therapy (PDT) treatment of cancer. The synthesis of two highly fluorescent BODIPY cores was achieved via the acid-catalysed condensation of a pyrrole and a functionalised aldehyde. In order to promote intersystem crossing, and hence improve the singlet oxygen generation of these dyes, bromine atoms were added at the 2,6-positions of the BODIPY core. These dibrominated analogues showed good singlet oxygen quantum yields, and excellent photostability in ethanol. In order to red-shift the main spectral bands of the BODIPY dyes towards the therapeutic window, vinyl/ styryl groups were introduced at the 3-, 5-, and 7-positions via a modified Knoevengal condensation reaction. The addition of vinyl/ styryl groups to the BODIPY core caused an increase in fluorescence quantum yield as well as a decrease in singlet oxygen quantum yield with respect to the dibrominated analogues. However, two of the red-shifted BODIPY dyes still showed moderate singlet oxygen quantum yields. The use of BODIPY dyes in nonlinear optics (NLO) was explored. The nonlinear optical characterisations and optical limiting properties of a series of 3,5-dithienylenevinylene BODIPY dyes were studied, both in dimethylformamide (DMF) solution and when embedded in poly(bisphenol A carbonate) (PBC) as thin films. The 3,5-dithienylenevinylene BODIPY dyes showed typical nonlinear absorption behaviour, with reverse saturable absorption (RSA) profiles, indicating that they have potential as optical limiters. The second-order hyperpolarizability (Y), and third-order nonlinear susceptibility (/m[/(3)]) values are also reported for these dyes. The optical limiting values of one of the BODIPY dyes in solution, and two of the BODIPY-embedded PBC films, were below the maximum threshold of 0.95 J-cm-2. The effect of addition of substituents on the electronic structure of the BODIPY dyes was investigated using TD-DFT calculations. The calculated trends closely followed those determined experimentally.
- Full Text:
- Date Issued: 2018
Characterisation of surfaces modified with phthalocyanines through click chemistry for applications in electrochemical sensing
- O'Donoghue, Charles St John Nqwabuko
- Authors: O'Donoghue, Charles St John Nqwabuko
- Date: 2018
- Subjects: Electrodes, Carbon , Phthalocyanines , X-ray photoelectron spectroscopy , Electrochemistry , Electrochemical sensors , Hydrazine , Click chemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/58046 , vital:27038
- Description: One form of surface modification was primarily investigated in this work on glassy carbon electrodes. The form of modification is comprised of a series of steps in which electrografting is first applied to the glassy carbon surface, which is then followed up with click chemistry to ultimately immobilise a phthalocyanine onto the surface. The modified glassy carbon electrodes and surfaces were characterised with a combination of scanning electrochemical microscopy, X-ray photoelectron spectroscopy and various electrochemical methods. In this work, three alkyne substituted phthalocyanines were used. Two novel phthalocyanines, with nickel and cobalt metal centres, were studied alongside a manganese phthalocyanine reported in literature. Each of the three phthalocyanines was modified at the peripheral position with a 1-hexyne group, via a glycosidic bond, yielding the terminal alkyne groups that were used for subsequent click reactions. In situ diazotisation was used to graft 4-azidoaniline groups to the surface of the glassy carbon electrode. The azide bearing 4- azidoaniline groups were thus used to anchor the tetra substituted phthalocyanines to the surface of the electrodes. This method yielded successful modification of the electrodes and lead to their application in sensing studies. The modified electrodes were primarily used to catalyse the common agricultural oxidising agent hydrazine.
- Full Text:
- Date Issued: 2018
- Authors: O'Donoghue, Charles St John Nqwabuko
- Date: 2018
- Subjects: Electrodes, Carbon , Phthalocyanines , X-ray photoelectron spectroscopy , Electrochemistry , Electrochemical sensors , Hydrazine , Click chemistry
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/58046 , vital:27038
- Description: One form of surface modification was primarily investigated in this work on glassy carbon electrodes. The form of modification is comprised of a series of steps in which electrografting is first applied to the glassy carbon surface, which is then followed up with click chemistry to ultimately immobilise a phthalocyanine onto the surface. The modified glassy carbon electrodes and surfaces were characterised with a combination of scanning electrochemical microscopy, X-ray photoelectron spectroscopy and various electrochemical methods. In this work, three alkyne substituted phthalocyanines were used. Two novel phthalocyanines, with nickel and cobalt metal centres, were studied alongside a manganese phthalocyanine reported in literature. Each of the three phthalocyanines was modified at the peripheral position with a 1-hexyne group, via a glycosidic bond, yielding the terminal alkyne groups that were used for subsequent click reactions. In situ diazotisation was used to graft 4-azidoaniline groups to the surface of the glassy carbon electrode. The azide bearing 4- azidoaniline groups were thus used to anchor the tetra substituted phthalocyanines to the surface of the electrodes. This method yielded successful modification of the electrodes and lead to their application in sensing studies. The modified electrodes were primarily used to catalyse the common agricultural oxidising agent hydrazine.
- Full Text:
- Date Issued: 2018
Development of a computational chemistry scheme for testing the utility of synthetic bacteriochlorin in dye-sensitized solar cells
- Authors: Kota, Ntsika
- Date: 2018
- Subjects: Dye-sensitized solar cells , Computational chemistry , Density functionals , Electronic excitation , Molecular orbitals , Oscillator strengths , Bacteriochlorin
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/62327 , vital:28155
- Description: A computational chemistry scheme, based on density functional theory, was developed for in silico testing of a few bacteriochlorin properties relevant to dye-sensitized solar cells. These properties included electronic excitation wavelengths, molecular orbital energy levels, and oscillator strengths among others. Comparisons were made among four species, using computational proxies for electron injection quantum yield and photo-induced current production. The proxy measures for current production (frontier orbital energy level and short circuit current) made consistent, though qualitative, predictions about the ranking of the four dyes. The proxy measures for electron injection quantum yield (change in planar dipole moment and density of states) made less categorical predictions about the ranking. Overall, the scheme singled out one dye as the worst, but made no conclusive predictions about the relative ranking of the other three. There was insufficient data for comparison of the ranking predictions with experiment.
- Full Text:
- Date Issued: 2018
- Authors: Kota, Ntsika
- Date: 2018
- Subjects: Dye-sensitized solar cells , Computational chemistry , Density functionals , Electronic excitation , Molecular orbitals , Oscillator strengths , Bacteriochlorin
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/62327 , vital:28155
- Description: A computational chemistry scheme, based on density functional theory, was developed for in silico testing of a few bacteriochlorin properties relevant to dye-sensitized solar cells. These properties included electronic excitation wavelengths, molecular orbital energy levels, and oscillator strengths among others. Comparisons were made among four species, using computational proxies for electron injection quantum yield and photo-induced current production. The proxy measures for current production (frontier orbital energy level and short circuit current) made consistent, though qualitative, predictions about the ranking of the four dyes. The proxy measures for electron injection quantum yield (change in planar dipole moment and density of states) made less categorical predictions about the ranking. Overall, the scheme singled out one dye as the worst, but made no conclusive predictions about the relative ranking of the other three. There was insufficient data for comparison of the ranking predictions with experiment.
- Full Text:
- Date Issued: 2018
Donor-acceptor effects on the optical limiting properties of BODIPY dyes
- Authors: Hlatshwayo, Zweli Thabiso
- Date: 2018
- Subjects: Dyes and dyeing -- Chemistry , Photosensitizing compounds -- Therapeutic use , Cancer -- Photochemotherapy , Upconversion nanoparticles (UCNPs)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/63368 , vital:28397
- Description: The main objectives of the research described in this thesis were firstly to synthesize and characterize a series of structurally related BODIPY dyes that are potentially suitable for use in applications, secondly to conjugate a carboxylic acid substituted BODIPY dye to amine-functionalized upconversion nanoparticles (UCNPs) through an amide bond to enable singlet oxygen production upon irradiation at 978 nm in the biological window for tissue penetration for biomedical applications, and thirdly to compare the nonlinear optical (NLO) properties of various BODIPY dyes to determine whether push-pull effects enhance their utility for optical limiting (OL) applications. Halogenated BODIPY cores with high singlet oxygen quantum yields were prepared, which absorb in the green portion of the visible region and making it difficult to treat deeper skin tumors in the context of photodynamic therapy (PDT) applications. UCNPs generally absorb in the near-infrared (NIR) region (978 nm), and this is advantageous because, this is where absorption by water, cells and tissues is minimized. NaYF4: Yb/Er/Gd UCNPs were synthesized, amine functionalized and successfully conjugated to a halogenated carboxylic acid functionalized BODIPY. This allowed for favorable Förster resonance energy transfer (FRET) since one of the emission wavelengths of the NaYF4: Yb/Er/Gd UCNPs overlaps with the main absorption band of the BODIPY at 540 nm. The conjugate was irradiated at 978 nm, but instability of the BODIPY dye was observed, which made singlet oxygen quantum yield determination impossible. An enhanced singlet oxygen quantum yield value was observed upon irradiation of the conjugate at 540 nm, suggesting that further studies of this system are warranted. The OL properties of BODIPY cores and dyes, which are π-extended at the 3,5-positions with styryl groups, were studied in a series of different organic solvents at 532 nm by using the z-scan technique on a nanosecond timescale. Many of the dyes were used to compare the effects of introducing electron donor and acceptor groups on the OL properties of the dyes. The dipole moments of these dyes were found to correlate with the OL response. The OL results indicate that BODIPY dyes with push-pull properties, which are π-extended at the 3,5-positions with styryl groups, can be considered as viable candidates for use in OL applications. The studies sought to establish the effect of ESA in the triplet manifold as compared to the singlet manifold in as far as the OL response is concerned. The most promising dyes were embedded in polystyrene thin films, and this was found to significantly enhance their OL properties.
- Full Text:
- Date Issued: 2018
- Authors: Hlatshwayo, Zweli Thabiso
- Date: 2018
- Subjects: Dyes and dyeing -- Chemistry , Photosensitizing compounds -- Therapeutic use , Cancer -- Photochemotherapy , Upconversion nanoparticles (UCNPs)
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/63368 , vital:28397
- Description: The main objectives of the research described in this thesis were firstly to synthesize and characterize a series of structurally related BODIPY dyes that are potentially suitable for use in applications, secondly to conjugate a carboxylic acid substituted BODIPY dye to amine-functionalized upconversion nanoparticles (UCNPs) through an amide bond to enable singlet oxygen production upon irradiation at 978 nm in the biological window for tissue penetration for biomedical applications, and thirdly to compare the nonlinear optical (NLO) properties of various BODIPY dyes to determine whether push-pull effects enhance their utility for optical limiting (OL) applications. Halogenated BODIPY cores with high singlet oxygen quantum yields were prepared, which absorb in the green portion of the visible region and making it difficult to treat deeper skin tumors in the context of photodynamic therapy (PDT) applications. UCNPs generally absorb in the near-infrared (NIR) region (978 nm), and this is advantageous because, this is where absorption by water, cells and tissues is minimized. NaYF4: Yb/Er/Gd UCNPs were synthesized, amine functionalized and successfully conjugated to a halogenated carboxylic acid functionalized BODIPY. This allowed for favorable Förster resonance energy transfer (FRET) since one of the emission wavelengths of the NaYF4: Yb/Er/Gd UCNPs overlaps with the main absorption band of the BODIPY at 540 nm. The conjugate was irradiated at 978 nm, but instability of the BODIPY dye was observed, which made singlet oxygen quantum yield determination impossible. An enhanced singlet oxygen quantum yield value was observed upon irradiation of the conjugate at 540 nm, suggesting that further studies of this system are warranted. The OL properties of BODIPY cores and dyes, which are π-extended at the 3,5-positions with styryl groups, were studied in a series of different organic solvents at 532 nm by using the z-scan technique on a nanosecond timescale. Many of the dyes were used to compare the effects of introducing electron donor and acceptor groups on the OL properties of the dyes. The dipole moments of these dyes were found to correlate with the OL response. The OL results indicate that BODIPY dyes with push-pull properties, which are π-extended at the 3,5-positions with styryl groups, can be considered as viable candidates for use in OL applications. The studies sought to establish the effect of ESA in the triplet manifold as compared to the singlet manifold in as far as the OL response is concerned. The most promising dyes were embedded in polystyrene thin films, and this was found to significantly enhance their OL properties.
- Full Text:
- Date Issued: 2018
Exploring the potential of imines as antiprotozoan agents with focus on t. Brucei and p. Falciparum
- Authors: Oluwafemi, Kola Augustus
- Date: 2018
- Subjects: Protozoa , Parasites , Imines , Nuclear magnetic resonance , HeLa cells , Plasmodium falciparum , Trypanosoma brucei , Isomerism
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/62235 , vital:28145 , DOI 10.21504/10962/62235
- Description: This work focuses on the design, synthesis and evaluation of imine-containing heterocyclic and acyclic compounds with special focus on their bioactivity against parasitic protozoans (P. falciparum and T. brucei) - given the context of drug resistance in the treatment of malaria and Human African sleeping sickness and the fact that several bioactive organic compounds have been reported to possess the imino group. Starting from 2-aminopyridine, novel #-alkylated-5-bromo-7-azabenzimidazoles and substituted 5-bromo-1-(carbamoylmethy)-7-azabenzimidazole derivatives were prepared, and their bioactivity against parasitic protozoans was assessed. NMR spectra of the substituted 5- bromo-1-(carbamoylmethy)-7-azabenzimidazole derivatives exhibited rotational isomerism, and a dynamic NMR study was used in the estimation of the rate constants and the free- energies of activation for rotation. The free-energy differences between the two rotamers were determined and the more stable conformations were predicted. Novel 2-phenyl-7-azabenzimidazoles were also synthesised from 2-aminopyridine. A convenient method for the regioselective formylation of 2,3-diaminopyridines into 2-amino- 7-(benzylimino)pyridine analogues of 2-phenyl-7-azabenzimidazole was developed, and some of the resulting imino derivatives were hydrogenated to verify the importance of the imino moiety for bioactivity. The 2-phenyl-7-azabenzimidazoles and the 2-amino-7- (benzylimino)pyridine analogues were screened for their anti-protozoal activity and their cytotoxicity level was determined against the HeLa cell line. In order to validate the importance of the pyridine moiety, novel #-(phenyl)-2- hydroxybenzylimines, #-(benzyl)-2-hydroxybenzylimines and (±)-trans-1,2-bis[2- hydroxybenzylimino]cyclohexanes were also synthesized and screened for activity against the parasitic protozoans and for cytotoxicity against the HeLa cell line. The biological assay results indicated that these compounds are not significantly cytotoxic and a good number of them show potential as lead compounds for the development of new malaria and trypanosomiasis drugs. , Thesis (PhD) -- Faculty of Science, Chemistry, 2018
- Full Text:
- Date Issued: 2018
- Authors: Oluwafemi, Kola Augustus
- Date: 2018
- Subjects: Protozoa , Parasites , Imines , Nuclear magnetic resonance , HeLa cells , Plasmodium falciparum , Trypanosoma brucei , Isomerism
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/62235 , vital:28145 , DOI 10.21504/10962/62235
- Description: This work focuses on the design, synthesis and evaluation of imine-containing heterocyclic and acyclic compounds with special focus on their bioactivity against parasitic protozoans (P. falciparum and T. brucei) - given the context of drug resistance in the treatment of malaria and Human African sleeping sickness and the fact that several bioactive organic compounds have been reported to possess the imino group. Starting from 2-aminopyridine, novel #-alkylated-5-bromo-7-azabenzimidazoles and substituted 5-bromo-1-(carbamoylmethy)-7-azabenzimidazole derivatives were prepared, and their bioactivity against parasitic protozoans was assessed. NMR spectra of the substituted 5- bromo-1-(carbamoylmethy)-7-azabenzimidazole derivatives exhibited rotational isomerism, and a dynamic NMR study was used in the estimation of the rate constants and the free- energies of activation for rotation. The free-energy differences between the two rotamers were determined and the more stable conformations were predicted. Novel 2-phenyl-7-azabenzimidazoles were also synthesised from 2-aminopyridine. A convenient method for the regioselective formylation of 2,3-diaminopyridines into 2-amino- 7-(benzylimino)pyridine analogues of 2-phenyl-7-azabenzimidazole was developed, and some of the resulting imino derivatives were hydrogenated to verify the importance of the imino moiety for bioactivity. The 2-phenyl-7-azabenzimidazoles and the 2-amino-7- (benzylimino)pyridine analogues were screened for their anti-protozoal activity and their cytotoxicity level was determined against the HeLa cell line. In order to validate the importance of the pyridine moiety, novel #-(phenyl)-2- hydroxybenzylimines, #-(benzyl)-2-hydroxybenzylimines and (±)-trans-1,2-bis[2- hydroxybenzylimino]cyclohexanes were also synthesized and screened for activity against the parasitic protozoans and for cytotoxicity against the HeLa cell line. The biological assay results indicated that these compounds are not significantly cytotoxic and a good number of them show potential as lead compounds for the development of new malaria and trypanosomiasis drugs. , Thesis (PhD) -- Faculty of Science, Chemistry, 2018
- Full Text:
- Date Issued: 2018