Octa carboxy metal (II) phthalocyanine covalent films as pH sensitive electrochemical sensor for neurotransmitters
- Authors: Moyo, Iphithuli
- Date: 2023-10-13
- Subjects: Phthalocyanines , Thin films , Neurotransmitters , Carboxylic acids
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/424525 , vital:72161
- Description: Octa acyl chloride metallophthalocyanines of cobalt (CoOAClPc) and iron (FeOAClPc) were synthesized and characterized using spectroscopic and electrochemical techniques. The metallophthalocyanines were fabricated as thin films onto phenylethylamine (PEA) pre-grafted Au electrode following a covalent amide reaction. The spectroscopic and electrochemical characterization confirmed the modification of the bare Au with PEA monolayer thin film (Au-PEA) and the covalent immobilization of MOAClPc to yield Au-PEA-MOAClPc (where M is Co and Fe). The acyl chloride functional groups were hydrolyzed forming pH sensitive thin films of terminal carboxylic acid (-COOH) functional groups (Au-PEA-MOCAPc). The Au-PEA-MOCAPc electrode exhibited pH selectivity and sensitivity properties towards the negatively charged [Fe(CN)6]3-/4- and positively charged [Ru(NH3)6]2+/3+ redox probes. The Au-PEA-MOCAPc electrodes were studied for their electrocatalytic and electroanalytical properties towards the detection of catecholamine neurotransmitters; dopamine (DA), epinephrine (EP) and norepinephrine (NOR). The electrodes were further investigated in the screening of ascorbic and uric acids by means of pH sensitive functional groups. The modification process exhibited good reproducibility. Excellent electrocatalytic and electroanalytical properties were observed. The limits of detection (LOD) determined using 3σ/m was found to be 64 nM, 0.22 μM and 0.17 μM for DA, EP and NOR respectively using Au-PEA-CoOCAPc. For Au-PEA-FeOCAPc, the LOD was found to 0.24 μM, 0.45 μM and 0.34 μM for DA, EP and NOR respectively. The Au-PEA-MOCAPc electrodes screened off the strong interferents, ascorbic and uric acid. The Au-PEA-FeOCAPc electrode was evaluated for its potential application in real sample analysis using new born calf serum, and it showed excellent percentage recoveries. , Thesis (MSc) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-10-13
- Authors: Moyo, Iphithuli
- Date: 2023-10-13
- Subjects: Phthalocyanines , Thin films , Neurotransmitters , Carboxylic acids
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/424525 , vital:72161
- Description: Octa acyl chloride metallophthalocyanines of cobalt (CoOAClPc) and iron (FeOAClPc) were synthesized and characterized using spectroscopic and electrochemical techniques. The metallophthalocyanines were fabricated as thin films onto phenylethylamine (PEA) pre-grafted Au electrode following a covalent amide reaction. The spectroscopic and electrochemical characterization confirmed the modification of the bare Au with PEA monolayer thin film (Au-PEA) and the covalent immobilization of MOAClPc to yield Au-PEA-MOAClPc (where M is Co and Fe). The acyl chloride functional groups were hydrolyzed forming pH sensitive thin films of terminal carboxylic acid (-COOH) functional groups (Au-PEA-MOCAPc). The Au-PEA-MOCAPc electrode exhibited pH selectivity and sensitivity properties towards the negatively charged [Fe(CN)6]3-/4- and positively charged [Ru(NH3)6]2+/3+ redox probes. The Au-PEA-MOCAPc electrodes were studied for their electrocatalytic and electroanalytical properties towards the detection of catecholamine neurotransmitters; dopamine (DA), epinephrine (EP) and norepinephrine (NOR). The electrodes were further investigated in the screening of ascorbic and uric acids by means of pH sensitive functional groups. The modification process exhibited good reproducibility. Excellent electrocatalytic and electroanalytical properties were observed. The limits of detection (LOD) determined using 3σ/m was found to be 64 nM, 0.22 μM and 0.17 μM for DA, EP and NOR respectively using Au-PEA-CoOCAPc. For Au-PEA-FeOCAPc, the LOD was found to 0.24 μM, 0.45 μM and 0.34 μM for DA, EP and NOR respectively. The Au-PEA-MOCAPc electrodes screened off the strong interferents, ascorbic and uric acid. The Au-PEA-FeOCAPc electrode was evaluated for its potential application in real sample analysis using new born calf serum, and it showed excellent percentage recoveries. , Thesis (MSc) -- Faculty of Science, Chemistry, 2023
- Full Text:
- Date Issued: 2023-10-13
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
Correlation of photovoltaics plant performance metrics
- Authors: Vumbugwa, Monphias
- Date: 2018
- Subjects: Photovoltaic cells , Perfomance -- Evaluation , Thin films
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/45657 , vital:38924
- Description: The generation of electrical energy using Photovoltaic (PV) technology has increased globally with the decrease in the cost of PV systems and the rise in electrical power demand. In South Africa, the support by the government in implementing the Renewable Energy Independent Power Producer Procurement Programme (REIPPPP) has seen a growth in PV system deployment and investment in roof and ground mounted, stand alone and grid connected PV plants. This rapid growth shows that the PV industry is becoming highly competitive as there is a shift to low carbon emissions and it is anticipated to be the most affordable source of electricity. Hence, there is need to develop maintenance and fault diagnosis expertise and capabilities in the PV industry, which can in turn improve the dependability, productiveness and lifespan of PV systems. Solar PV modules directly receive and convert solar irradiance into electricity and may not generate the expected optimum energy due to abnormalities which arise when they are exposed to harsh unfavorable environmental conditions in the field. Thermal Infrared (TIR) imaging is widely used as a fault diagnosis tool in operating PV modules and mostly in large PV power plants. Therefore, there is need to research the interpretation of the observed thermal signatures and the impact that the anomalies have on electrical output of the system so as to improve the PV maintenance systems. This research focuses on identifying performance limiting defects using an Infra-Red (I-R) camera, mounted on an Unmanned Aerial Vehicle (UAV), to understand the effect of thermal signatures on current-voltage (I-V) characteristics of PV module strings. Aerial TIR imaging using a UAV can rapidly identify abnormalities in operational PV modules strings as hotspots. Any deviation of the string I-V curve, from the expected, indicates a problem with one or more PV modules in the string. However, locating the faulty module involves measuring I-V parameters of the individual modules in a string, which is not feasible in large PV power plants. Therefore, there is a need to estimate the power loss associated with the thermal signatures in PV module strings. Visual inspection may help in identifying the exact cause of some hotspots, while other hotspots need special characterization techniques, such as Electroluminescence (EL) and UV Fluorescence (UV-F), which can indicate if a solar cell is cracked or has weak busbars or contact finger connections.
- Full Text:
- Date Issued: 2018
- Authors: Vumbugwa, Monphias
- Date: 2018
- Subjects: Photovoltaic cells , Perfomance -- Evaluation , Thin films
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/45657 , vital:38924
- Description: The generation of electrical energy using Photovoltaic (PV) technology has increased globally with the decrease in the cost of PV systems and the rise in electrical power demand. In South Africa, the support by the government in implementing the Renewable Energy Independent Power Producer Procurement Programme (REIPPPP) has seen a growth in PV system deployment and investment in roof and ground mounted, stand alone and grid connected PV plants. This rapid growth shows that the PV industry is becoming highly competitive as there is a shift to low carbon emissions and it is anticipated to be the most affordable source of electricity. Hence, there is need to develop maintenance and fault diagnosis expertise and capabilities in the PV industry, which can in turn improve the dependability, productiveness and lifespan of PV systems. Solar PV modules directly receive and convert solar irradiance into electricity and may not generate the expected optimum energy due to abnormalities which arise when they are exposed to harsh unfavorable environmental conditions in the field. Thermal Infrared (TIR) imaging is widely used as a fault diagnosis tool in operating PV modules and mostly in large PV power plants. Therefore, there is need to research the interpretation of the observed thermal signatures and the impact that the anomalies have on electrical output of the system so as to improve the PV maintenance systems. This research focuses on identifying performance limiting defects using an Infra-Red (I-R) camera, mounted on an Unmanned Aerial Vehicle (UAV), to understand the effect of thermal signatures on current-voltage (I-V) characteristics of PV module strings. Aerial TIR imaging using a UAV can rapidly identify abnormalities in operational PV modules strings as hotspots. Any deviation of the string I-V curve, from the expected, indicates a problem with one or more PV modules in the string. However, locating the faulty module involves measuring I-V parameters of the individual modules in a string, which is not feasible in large PV power plants. Therefore, there is a need to estimate the power loss associated with the thermal signatures in PV module strings. Visual inspection may help in identifying the exact cause of some hotspots, while other hotspots need special characterization techniques, such as Electroluminescence (EL) and UV Fluorescence (UV-F), which can indicate if a solar cell is cracked or has weak busbars or contact finger connections.
- Full Text:
- Date Issued: 2018
Nonlinear optical studies of phthalocyanines and triazatetrabenzcorroles in solution and in thin films
- Authors: Mkhize, Nhlakanipho Colin
- Date: 2015
- Subjects: Phthalocyanines , Thin films , Nonlinear optics , Phosphorus
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4542 , http://hdl.handle.net/10962/d1017922
- Description: This work presents photophysical and nonlinear optical properties of a novel Cd 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (CdOtBPPc) and compared with those of Pb 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (PbOtBPPc). For both the CdOtBPPc and PbOtBPPc, third order imaginary susceptibility and second order hyperpolarizability values were found to be within the limit set for good optical limiters. The Pcs were embedded in poly (methyl methacrylate) (PMMA) and poly(bisphenol A carbonate) (PBC) as thin films. The optical limiting values of the Pcs once embedded in film were found to be greatly improved and the limiting intensity of each film was well below the maximum threshold. Both PbOtBPPc and CdOtBPPc showed better optical limiting when embedded in PBC compared to PMMA. CdOtBPPc shows better nonlinear optical behaviour than PbOtBPPc in solution and as thin films, even though the former is aggregated in solution. Novel phosphorus triazatetrabenzcorroles (TBC) tetrasubstituted at the α- and β- and octa substituted at the β- positions of the peripheral fused benzene rings with t-butylphenoxy substituents were prepared and characterized. The effects of the substituents and the missing aza-nitrogen on the electronic structures and optical spectroscopy are investigated with TD-DFT calculations and MCD spectroscopy. The optical limiting properties were investigated to examine whether the lower symmetry that results from the direct pyrrole-pyrrole bond and hence the permanent dipole moment that is introduced result in higher safety thresholds, relative to the values that have been reported for phthalocyanines. The suitability of the compounds for singlet oxygen applications has also been examined. Novel phosphorus phthalocyanines, analogous to the triazatetrabenzcorroles were also investigated. Due to their high photodegradation quantum yield however, only the fluorescence quantum yields and lifetimes were able to be determined.
- Full Text:
- Date Issued: 2015
- Authors: Mkhize, Nhlakanipho Colin
- Date: 2015
- Subjects: Phthalocyanines , Thin films , Nonlinear optics , Phosphorus
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4542 , http://hdl.handle.net/10962/d1017922
- Description: This work presents photophysical and nonlinear optical properties of a novel Cd 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (CdOtBPPc) and compared with those of Pb 2,3-[octakis{4-tert-butylphenoxyphthalocyanine}] (PbOtBPPc). For both the CdOtBPPc and PbOtBPPc, third order imaginary susceptibility and second order hyperpolarizability values were found to be within the limit set for good optical limiters. The Pcs were embedded in poly (methyl methacrylate) (PMMA) and poly(bisphenol A carbonate) (PBC) as thin films. The optical limiting values of the Pcs once embedded in film were found to be greatly improved and the limiting intensity of each film was well below the maximum threshold. Both PbOtBPPc and CdOtBPPc showed better optical limiting when embedded in PBC compared to PMMA. CdOtBPPc shows better nonlinear optical behaviour than PbOtBPPc in solution and as thin films, even though the former is aggregated in solution. Novel phosphorus triazatetrabenzcorroles (TBC) tetrasubstituted at the α- and β- and octa substituted at the β- positions of the peripheral fused benzene rings with t-butylphenoxy substituents were prepared and characterized. The effects of the substituents and the missing aza-nitrogen on the electronic structures and optical spectroscopy are investigated with TD-DFT calculations and MCD spectroscopy. The optical limiting properties were investigated to examine whether the lower symmetry that results from the direct pyrrole-pyrrole bond and hence the permanent dipole moment that is introduced result in higher safety thresholds, relative to the values that have been reported for phthalocyanines. The suitability of the compounds for singlet oxygen applications has also been examined. Novel phosphorus phthalocyanines, analogous to the triazatetrabenzcorroles were also investigated. Due to their high photodegradation quantum yield however, only the fluorescence quantum yields and lifetimes were able to be determined.
- Full Text:
- Date Issued: 2015
A raman spectroscopy study of semiconducting thin films
- Authors: Goosen, William Edward
- Date: 2006
- Subjects: Raman spectroscopy , Semiconductor films , Thin films
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10514 , http://hdl.handle.net/10948/426 , Raman spectroscopy , Semiconductor films , Thin films
- Description: A home-built Raman system, utilizing a pseudo-backscattering geometry, was built in the Physics Department at the Nelson Mandela Metropolitan University (NMMU). The system was then used to analyse a variety of bulk and thin film semiconducting materials currently being studied in the Physics Department. Silicon wafers were exposed to hydrogen plasma. Raman analysis of hydrogen induced platelets (HIPs), resulting from hydrogen plasma treatment of silicon, is reported. ZnO layers were deposited on glass, GaAs, Si, sapphire and SiC-Si substrates by metalorganic chemical vapour deposition (MOCVD) in the Physics Department at the NMMU. It was found that the ZnO layers grown by MOCVD all exhibited a strong E2 (high) phonon mode that dominated the Raman spectra. Furthermore, the spectra lacked the A1 (LO) phonon mode which is usually associated with the O-vacancy, the Zn-interstitial, or complexes of the two, indicating that the layers were all of good quality. The influence of depositing the ZnO thin film on a 3 mm thick SiC layer was also investigated and compared with the deposition of ZnO on Si substrate, in order to reduce the lattice mismatch between ZnO and the Si substrate. The possible shift of the Raman peaks due to the residual strain in the film, if present, could not be resolved. Characterization of GaN and AlxGa1-xN produced by MOCVD at the CRHEA laboratory of the CNRS in Valbonne, France is reported. A sharp peak at 567 cm-1 corresponding to the E2 (high) mode of GaN broadens and shifts to higher wavenumbers as the aluminium content of the AlxGa1-xN is increased. The shift is accompanied by a decrease in the intensity and a broadening of this peak. The broadening was attributed to a general decrease in the quality of the layers which accompanies increased aluminium content in AlxGa1-xN.
- Full Text:
- Date Issued: 2006
- Authors: Goosen, William Edward
- Date: 2006
- Subjects: Raman spectroscopy , Semiconductor films , Thin films
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10514 , http://hdl.handle.net/10948/426 , Raman spectroscopy , Semiconductor films , Thin films
- Description: A home-built Raman system, utilizing a pseudo-backscattering geometry, was built in the Physics Department at the Nelson Mandela Metropolitan University (NMMU). The system was then used to analyse a variety of bulk and thin film semiconducting materials currently being studied in the Physics Department. Silicon wafers were exposed to hydrogen plasma. Raman analysis of hydrogen induced platelets (HIPs), resulting from hydrogen plasma treatment of silicon, is reported. ZnO layers were deposited on glass, GaAs, Si, sapphire and SiC-Si substrates by metalorganic chemical vapour deposition (MOCVD) in the Physics Department at the NMMU. It was found that the ZnO layers grown by MOCVD all exhibited a strong E2 (high) phonon mode that dominated the Raman spectra. Furthermore, the spectra lacked the A1 (LO) phonon mode which is usually associated with the O-vacancy, the Zn-interstitial, or complexes of the two, indicating that the layers were all of good quality. The influence of depositing the ZnO thin film on a 3 mm thick SiC layer was also investigated and compared with the deposition of ZnO on Si substrate, in order to reduce the lattice mismatch between ZnO and the Si substrate. The possible shift of the Raman peaks due to the residual strain in the film, if present, could not be resolved. Characterization of GaN and AlxGa1-xN produced by MOCVD at the CRHEA laboratory of the CNRS in Valbonne, France is reported. A sharp peak at 567 cm-1 corresponding to the E2 (high) mode of GaN broadens and shifts to higher wavenumbers as the aluminium content of the AlxGa1-xN is increased. The shift is accompanied by a decrease in the intensity and a broadening of this peak. The broadening was attributed to a general decrease in the quality of the layers which accompanies increased aluminium content in AlxGa1-xN.
- Full Text:
- Date Issued: 2006
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