Determination of nonlinear optical properties of phthalocyanine regioisomers using computational models
- Date: 2020
- Subjects: Electrochemistry , Phthalocyanines , Nanoparticles , Nonlinear optics , Nonlinear optical spectroscopy , Refraction
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/166197 , vital:41337
- Description: This work investigates the effects of the nonlinear optical properties of four different constitutional isomers (C4h, C2v, Cs, and D2h) of a series of tetrasubstituted phthalocyanines (free-base 3-4-tert-butylphenoxyether phthalocyanines, free-base 4-4-tertbutylphenoxyether phthalocyanines, SnCl2 tetra substituted 3-4-tert-butylphenoxyether phthalocyanine, and SnCl2 tetra substituted 4-4-tert-butylphenoxyether phthalocyanine). The properties investigated were the real and imaginary components of the 3rd order hyperpolarizability, as well as the excited state absorption and refraction cross sections. The investigations were performed with a z-scan over a range of laser beam intensities. This work determined the imaginary component of the 3rd order hyperpolarizability for the free-base and SnCl2 3-4-tert-butylphenoxyether phthalocyanines and 4-4-tert-butylphenoxyether phthalocyanines to be highly dependent on the excited state cross sections. The refraction caused due to the real component of the 3rd order hyperpolarizability of the phthalocyanines was also investigated, however, the values found were strongly dependent on the laser beam intensity and the cause of this was investigated. A Five-level model was developed and run on GPGPU computing devices in order to isolate the absorption and refractive cross sections. Theeffects of the regio substitution on the excited state cross sections were also investigated, and the 1st singlet excited state and 1st triplet state absorption cross sections were calculated for all constitutional isomers. It was found that the symmetry of the constitutional isomers have a disproportionately large effect on the excited state absorption when compared to the ground state absorption. The nonlinear refractive properties of all constitutional isomers were also investigated, and the values of the parametric susceptibility are reported herein. The nonlinear refraction was found to have less effect than was seen in the nonlinear absorption. The 1st singlet excited state and 1st triplet state refractive cross sections of all constitutional isomer was determined. The results indicated that if more than one excited state was present and contributing to the nonlinear refraction, then more data than was collected here would be required. However, the 1st singlet excited state cross section were successfully determined for the free-base constitutional isomers. This work concluded that the region substitution affected the excited states more than the ground state.
- Full Text:
- Date Issued: 2020
- Date: 2020
- Subjects: Electrochemistry , Phthalocyanines , Nanoparticles , Nonlinear optics , Nonlinear optical spectroscopy , Refraction
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/166197 , vital:41337
- Description: This work investigates the effects of the nonlinear optical properties of four different constitutional isomers (C4h, C2v, Cs, and D2h) of a series of tetrasubstituted phthalocyanines (free-base 3-4-tert-butylphenoxyether phthalocyanines, free-base 4-4-tertbutylphenoxyether phthalocyanines, SnCl2 tetra substituted 3-4-tert-butylphenoxyether phthalocyanine, and SnCl2 tetra substituted 4-4-tert-butylphenoxyether phthalocyanine). The properties investigated were the real and imaginary components of the 3rd order hyperpolarizability, as well as the excited state absorption and refraction cross sections. The investigations were performed with a z-scan over a range of laser beam intensities. This work determined the imaginary component of the 3rd order hyperpolarizability for the free-base and SnCl2 3-4-tert-butylphenoxyether phthalocyanines and 4-4-tert-butylphenoxyether phthalocyanines to be highly dependent on the excited state cross sections. The refraction caused due to the real component of the 3rd order hyperpolarizability of the phthalocyanines was also investigated, however, the values found were strongly dependent on the laser beam intensity and the cause of this was investigated. A Five-level model was developed and run on GPGPU computing devices in order to isolate the absorption and refractive cross sections. Theeffects of the regio substitution on the excited state cross sections were also investigated, and the 1st singlet excited state and 1st triplet state absorption cross sections were calculated for all constitutional isomers. It was found that the symmetry of the constitutional isomers have a disproportionately large effect on the excited state absorption when compared to the ground state absorption. The nonlinear refractive properties of all constitutional isomers were also investigated, and the values of the parametric susceptibility are reported herein. The nonlinear refraction was found to have less effect than was seen in the nonlinear absorption. The 1st singlet excited state and 1st triplet state refractive cross sections of all constitutional isomer was determined. The results indicated that if more than one excited state was present and contributing to the nonlinear refraction, then more data than was collected here would be required. However, the 1st singlet excited state cross section were successfully determined for the free-base constitutional isomers. This work concluded that the region substitution affected the excited states more than the ground state.
- Full Text:
- Date Issued: 2020
Synthesis, characterisation and electrocatalytic behaviour of three series of Metal Organic Frameworks
- Authors: Murinzi, Tafadzwa Wendy
- Date: 2020
- Subjects: Electrochemistry , Metal-organic frameworks , Polyoxometalates , Fourier transform infrared spectroscopy , Electrocatalysis , Cysteine
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/167598 , vital:41495
- Description: Metal organic frameworks (MOFs) have received a lot of attention over the past few years due to their vast range of interesting properties and applications, such as catalysis, environmental sensing and storage. This wide range of potential applications is afforded by careful selection and manipulation of the components chosen in assembling of MOFs. In this study, three series of MOFs were synthesized from Co(II), Cu(II) and Mo(VI) polyoxometallates with either 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid or 2,6- pyridinedicarboxylic acid as the ligands. In series 1, the common 1,3,5- benzenetricarboxylic acid MOF, HKUST-1, and POM modified HKUST-1 compounds involving encapsulation and encorporation of the POM were utilised. In series 2, flexible cobalt(II) benzenepolycarboxylate MOFs which investigated the effect of varying the degree of carboxylate substituent were utilised. In series 3, flexibly reduced heterocyclic polycarboxylate MOFs using 2,6-pyridine dicarboxylate were utilised. Solvothermal and slow evaporation synthesis conditions were employed. Where single crystals of good quality were produced, single crystal X-ray diffraction (SC-XRD) was employed for structural elucidation. In the absence of such crystals, a combination of elemental analysis, inductively coupled plasma optical emission spectrometry (ICP-OES) and powder X-ray diffraction (PXRD) was used. Characterization of the MOFs was done by Fourier transform infrared spectrometry (FTIR) and thermal methods, namely thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The electrocatalytic potential of the compounds in the oxidation of L-cysteine was then investigated using a variety of techniques. Cyclic voltammetry was used for L-cysteine detection whilst chronoamperometry and differential pulse voltammetry were used to determine the nanoprobes’ sensitivity, rate constants and detection limits. Electrochemical impedence spectroscopy was used to investigate the charge transfer resistance (RCT) and electron transfer kinetics. Of the three, series 3 gave the best signals and sensitivities for electrocatalysis of L-cysteine followed by series 2 and lastly series 1. Series 2 showed the highest stability and series 1 required the least overpotential. The results highlight the effects of different metal centres and ligands on electrocatalysis. The application of MOFs in electrochemistry is a relatively new field making the findings of this study a significant addition to the body of knowledge.
- Full Text:
- Date Issued: 2020
- Authors: Murinzi, Tafadzwa Wendy
- Date: 2020
- Subjects: Electrochemistry , Metal-organic frameworks , Polyoxometalates , Fourier transform infrared spectroscopy , Electrocatalysis , Cysteine
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/167598 , vital:41495
- Description: Metal organic frameworks (MOFs) have received a lot of attention over the past few years due to their vast range of interesting properties and applications, such as catalysis, environmental sensing and storage. This wide range of potential applications is afforded by careful selection and manipulation of the components chosen in assembling of MOFs. In this study, three series of MOFs were synthesized from Co(II), Cu(II) and Mo(VI) polyoxometallates with either 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid or 2,6- pyridinedicarboxylic acid as the ligands. In series 1, the common 1,3,5- benzenetricarboxylic acid MOF, HKUST-1, and POM modified HKUST-1 compounds involving encapsulation and encorporation of the POM were utilised. In series 2, flexible cobalt(II) benzenepolycarboxylate MOFs which investigated the effect of varying the degree of carboxylate substituent were utilised. In series 3, flexibly reduced heterocyclic polycarboxylate MOFs using 2,6-pyridine dicarboxylate were utilised. Solvothermal and slow evaporation synthesis conditions were employed. Where single crystals of good quality were produced, single crystal X-ray diffraction (SC-XRD) was employed for structural elucidation. In the absence of such crystals, a combination of elemental analysis, inductively coupled plasma optical emission spectrometry (ICP-OES) and powder X-ray diffraction (PXRD) was used. Characterization of the MOFs was done by Fourier transform infrared spectrometry (FTIR) and thermal methods, namely thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The electrocatalytic potential of the compounds in the oxidation of L-cysteine was then investigated using a variety of techniques. Cyclic voltammetry was used for L-cysteine detection whilst chronoamperometry and differential pulse voltammetry were used to determine the nanoprobes’ sensitivity, rate constants and detection limits. Electrochemical impedence spectroscopy was used to investigate the charge transfer resistance (RCT) and electron transfer kinetics. Of the three, series 3 gave the best signals and sensitivities for electrocatalysis of L-cysteine followed by series 2 and lastly series 1. Series 2 showed the highest stability and series 1 required the least overpotential. The results highlight the effects of different metal centres and ligands on electrocatalysis. The application of MOFs in electrochemistry is a relatively new field making the findings of this study a significant addition to the body of knowledge.
- Full Text:
- Date Issued: 2020
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
Electrode surface modification using metallophthalocyanines and metal nanoparticles : electrocatalytic activity
- Authors: Maringa, Audacity
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Electrocatalysis , Scanning electron microscopy , X-ray photoelectron spectroscopy , Electrochemistry , Scanning electrochemical microscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4541 , http://hdl.handle.net/10962/d1017921
- Description: Metallophthalocyanines and metal nanoparticles were successfully synthesized and applied for the electrooxidation of amitrole, nitrite and hydrazine individually or when employed together. The synthesized materials were characterized using the following techniques: predominantly scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electrochemistry and scanning electrochemical microscopy (SECM). Different electrode modification methods were used to modify the glassy carbon substrates. The methods include adsorption, electrodeposition, electropolymerization and click chemistry. Modifying the glassy carbon substrate with MPc (electropolymerization) followed by metal nanoparticles (electrodeposition) or vice versa, made a hybrid modified surface that had efficient electron transfer. This was confirmed by electrochemical impedance studies with voltammetry measurements having lower detection potentials for the analytes. This work also describes for the first time the micropatterning of the glassy carbon substrate using the SECM tip. The substrate was electrografted with 4-azidobenzenediazonium salt and then the click reaction was performed using ethynylferrocene facilitated by Cu⁺ produced at the SECM tip. The SECM imaging was then used to show the clicked spot.
- Full Text:
- Date Issued: 2015
- Authors: Maringa, Audacity
- Date: 2015
- Subjects: Phthalocyanines , Nanoparticles , Electrocatalysis , Scanning electron microscopy , X-ray photoelectron spectroscopy , Electrochemistry , Scanning electrochemical microscopy
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4541 , http://hdl.handle.net/10962/d1017921
- Description: Metallophthalocyanines and metal nanoparticles were successfully synthesized and applied for the electrooxidation of amitrole, nitrite and hydrazine individually or when employed together. The synthesized materials were characterized using the following techniques: predominantly scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electrochemistry and scanning electrochemical microscopy (SECM). Different electrode modification methods were used to modify the glassy carbon substrates. The methods include adsorption, electrodeposition, electropolymerization and click chemistry. Modifying the glassy carbon substrate with MPc (electropolymerization) followed by metal nanoparticles (electrodeposition) or vice versa, made a hybrid modified surface that had efficient electron transfer. This was confirmed by electrochemical impedance studies with voltammetry measurements having lower detection potentials for the analytes. This work also describes for the first time the micropatterning of the glassy carbon substrate using the SECM tip. The substrate was electrografted with 4-azidobenzenediazonium salt and then the click reaction was performed using ethynylferrocene facilitated by Cu⁺ produced at the SECM tip. The SECM imaging was then used to show the clicked spot.
- Full Text:
- Date Issued: 2015
Electrochemical sensing and immunosensing using metallophthalocyanines and biomolecular modified surfaces
- Authors: Mashazi, Philani Nkosinathi
- Date: 2012
- Subjects: Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Measles -- Measurement
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5580 , http://hdl.handle.net/10962/d1018248
- Description: The synthesis of cobalt and manganese phthalocyanine complexes bearing eight hexylthio and four amino substituents was carried out. The formation of thin films of these complexes using different modification methods was also studied. Hexylthio functionalized metallophthalocyanine complexes were immobilized onto gold electrode surfaces using the self-assembly techniques. Surface modifications using cobalt and manganese tetraamino phthalocyanine as polymers, monolayers (onto electrografted surfaces) and as carbon nanotube – metallophthalocyanine conjugates was also carried out. The new method of modifying gold electrodes with metal tetraamino phthalocyanine complexes was investigated. The modified electrode surfaces were studied for their electrocatalytic properties and as potential electrochemical sensors for the detection of hydrogen peroxide (H₂O₂). The limits of detection for the H₂O₂ were of the orders of ~10⁻⁷ M for all the modified electrodes. The modified electrodes gave very good analytical parameters; such as good sensitivity, linearity at studied concentration range and well-defined analytical peaks with increased current densities. The modification methods were reproducible, highly conducting thin films were formed and the modified electrodes were very stable. The design of electrochemical immunosensors for the detection of measles-specific antibodies was also carried out. The modified surface with measles-antigen as sensing element was accomplished using covalent immobilization for an intimate connection of the measles-antigen as a sensing layer onto an electrode surface. Two methods of detecting measles-specific antibodies were investigated and these methods were based on electrochemical impedance, i.e. label-free detection, and voltammetric method using horse-radish peroxidase (HRP) labeled antibody as a reporter. The detection of measles-specific antibodies was accomplished using both these methods. The potential applications of the designed immunosensor were evaluated in real samples (human and newborn calf serum) and the electrodes could detect the antibodies in the complex sample matrix with ease.
- Full Text:
- Date Issued: 2012
- Authors: Mashazi, Philani Nkosinathi
- Date: 2012
- Subjects: Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Measles -- Measurement
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:5580 , http://hdl.handle.net/10962/d1018248
- Description: The synthesis of cobalt and manganese phthalocyanine complexes bearing eight hexylthio and four amino substituents was carried out. The formation of thin films of these complexes using different modification methods was also studied. Hexylthio functionalized metallophthalocyanine complexes were immobilized onto gold electrode surfaces using the self-assembly techniques. Surface modifications using cobalt and manganese tetraamino phthalocyanine as polymers, monolayers (onto electrografted surfaces) and as carbon nanotube – metallophthalocyanine conjugates was also carried out. The new method of modifying gold electrodes with metal tetraamino phthalocyanine complexes was investigated. The modified electrode surfaces were studied for their electrocatalytic properties and as potential electrochemical sensors for the detection of hydrogen peroxide (H₂O₂). The limits of detection for the H₂O₂ were of the orders of ~10⁻⁷ M for all the modified electrodes. The modified electrodes gave very good analytical parameters; such as good sensitivity, linearity at studied concentration range and well-defined analytical peaks with increased current densities. The modification methods were reproducible, highly conducting thin films were formed and the modified electrodes were very stable. The design of electrochemical immunosensors for the detection of measles-specific antibodies was also carried out. The modified surface with measles-antigen as sensing element was accomplished using covalent immobilization for an intimate connection of the measles-antigen as a sensing layer onto an electrode surface. Two methods of detecting measles-specific antibodies were investigated and these methods were based on electrochemical impedance, i.e. label-free detection, and voltammetric method using horse-radish peroxidase (HRP) labeled antibody as a reporter. The detection of measles-specific antibodies was accomplished using both these methods. The potential applications of the designed immunosensor were evaluated in real samples (human and newborn calf serum) and the electrodes could detect the antibodies in the complex sample matrix with ease.
- Full Text:
- Date Issued: 2012
Nanomaterial modified electrodes : optimization of voltammetric sensors for pharmaceutical and industrial application
- Authors: Brimecombe, Rory Dennis
- Date: 2011
- Subjects: Voltammetry , Electrochemistry , Nanotubes , Nanostructured materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4101 , http://hdl.handle.net/10962/d1009721
- Description: Nanomaterials, in particular carbon nanotubes have been shown to exhibit favourable properties for the enhancement of electrochemical detection of target analytes in complex matrices. There is however scope for improvement in terms of the optimization thereof in electrochemical sensors surface modification. The aim of this thesis was to examine methods that would result in increased current response, lowered passivation and application of such modified surfaces with application to pharmaceutically and industrially relevant analytes. Current methods for enhancing the performance of carbon nanotubes include acid functionalization which not only increases the hydrophilicity of the nanotubes, and consequently their ability to provide stable (aqueous) suspensions, but also introduces electrochemically active sites. This particular approach is however not normalized in the literature. Over-exposure to acid treatment results in loss of structural integrity of the carbon nanotubes, and as such a fine balance exists between achieving these dual outcomes. Guided by high resolution scanning electron microscopy, atomic force microscopy, voltammetric and impedance studies, this thesis examined the role of the length of time of the acid functionalization process as well as the impact of activation of carbon nanotubes and fullerenes on electrochemical sensor performance. Based on desired charge transfer resistances, rate transfer coefficients and sensitivity towards redox probes the optimal length of acid functionalization for multiwalled carbon nanotubes was 9 hours and 4 hours for single-walled carbon nanotubes. Further improvements in the desired outcomes were achieved through electrochemical activation of the modified electrode surface by cycling in the presence of catechol, in a novel approach. By employing electrochemical impedance spectroscopy it was observed that catechol activation resulted in lowered charge transfer resistance, before and after activation, with functionalized multi-walled carbon nanotubes (9 hours) exhibiting the greatest decrease of 90 % and functionalized single-walled carbon nanotubes (4 hours), a 50 % decrease. Corresponding increases in the heterologous rate transfer coefficient showed a 770 % increase for functionalized multi-walled carbon nanotubes (9 hours), following catechol activation. Comparative observations for fullerenes following partial reduction in potassium hydroxide yielded a 30 % decrease in charge transfer resistance, with an increased heterologous rate transfer coefficient at a fullerene modified surface The performance of the nanomaterial modified electrodes was applied to the detection of wortmannin with applications in bioprocess control and in the pharmaceutical sector as well as to the detection and monitoring of the industrial dye Reactive red. Of particular relevance to these analytes was the assessment of the nanomaterial modified electrodes for enhanced stability, reproducibility, sensitivity and decreased passivation effects. In this study the first known account of wortmannin detection through electrochemical methods is reported. Voltammetric characterization of wortmannin revealed an irreversible cathodic process with a total number of 4 electrons and a diffusion coefficient of 1.19 x 10-7 cm².s⁻¹. At a functionalized multiwalled carbon nanotubes modified glassy carbon electrode a limit of detection of 0.128 nmol.cm⁻³ was obtained, and with limited surface passivation the detection scheme afforded pertinent analyses in biological media representing a substantial improvement over chromatographic detection methods. This study also provided the first account of the voltammetric detection of reactive red, competing favourably with traditional spectroscopic methods for monitoring biodegradation of this compound in real time.
- Full Text:
- Date Issued: 2011
- Authors: Brimecombe, Rory Dennis
- Date: 2011
- Subjects: Voltammetry , Electrochemistry , Nanotubes , Nanostructured materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4101 , http://hdl.handle.net/10962/d1009721
- Description: Nanomaterials, in particular carbon nanotubes have been shown to exhibit favourable properties for the enhancement of electrochemical detection of target analytes in complex matrices. There is however scope for improvement in terms of the optimization thereof in electrochemical sensors surface modification. The aim of this thesis was to examine methods that would result in increased current response, lowered passivation and application of such modified surfaces with application to pharmaceutically and industrially relevant analytes. Current methods for enhancing the performance of carbon nanotubes include acid functionalization which not only increases the hydrophilicity of the nanotubes, and consequently their ability to provide stable (aqueous) suspensions, but also introduces electrochemically active sites. This particular approach is however not normalized in the literature. Over-exposure to acid treatment results in loss of structural integrity of the carbon nanotubes, and as such a fine balance exists between achieving these dual outcomes. Guided by high resolution scanning electron microscopy, atomic force microscopy, voltammetric and impedance studies, this thesis examined the role of the length of time of the acid functionalization process as well as the impact of activation of carbon nanotubes and fullerenes on electrochemical sensor performance. Based on desired charge transfer resistances, rate transfer coefficients and sensitivity towards redox probes the optimal length of acid functionalization for multiwalled carbon nanotubes was 9 hours and 4 hours for single-walled carbon nanotubes. Further improvements in the desired outcomes were achieved through electrochemical activation of the modified electrode surface by cycling in the presence of catechol, in a novel approach. By employing electrochemical impedance spectroscopy it was observed that catechol activation resulted in lowered charge transfer resistance, before and after activation, with functionalized multi-walled carbon nanotubes (9 hours) exhibiting the greatest decrease of 90 % and functionalized single-walled carbon nanotubes (4 hours), a 50 % decrease. Corresponding increases in the heterologous rate transfer coefficient showed a 770 % increase for functionalized multi-walled carbon nanotubes (9 hours), following catechol activation. Comparative observations for fullerenes following partial reduction in potassium hydroxide yielded a 30 % decrease in charge transfer resistance, with an increased heterologous rate transfer coefficient at a fullerene modified surface The performance of the nanomaterial modified electrodes was applied to the detection of wortmannin with applications in bioprocess control and in the pharmaceutical sector as well as to the detection and monitoring of the industrial dye Reactive red. Of particular relevance to these analytes was the assessment of the nanomaterial modified electrodes for enhanced stability, reproducibility, sensitivity and decreased passivation effects. In this study the first known account of wortmannin detection through electrochemical methods is reported. Voltammetric characterization of wortmannin revealed an irreversible cathodic process with a total number of 4 electrons and a diffusion coefficient of 1.19 x 10-7 cm².s⁻¹. At a functionalized multiwalled carbon nanotubes modified glassy carbon electrode a limit of detection of 0.128 nmol.cm⁻³ was obtained, and with limited surface passivation the detection scheme afforded pertinent analyses in biological media representing a substantial improvement over chromatographic detection methods. This study also provided the first account of the voltammetric detection of reactive red, competing favourably with traditional spectroscopic methods for monitoring biodegradation of this compound in real time.
- Full Text:
- Date Issued: 2011
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