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
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
Synthesis and electrochemistry of octapentylthio phthalocyanine complexes of manganese, titanium and vanadium
- Authors: Mbambisa, Gcineka
- Date: 2009
- Subjects: Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4368 , http://hdl.handle.net/10962/d1005033 , Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Description: Synthesis of new thio derivatised Pcs with manganese, titanium and vanadium as a central metal is reported. The complexes synthesised were characterised using spectroscopic and electrochemical means. The complexes displayed interesting spectroscopic properties with absorption of the Q band being observed in the near infrared region. These complexes have unusual colours for MPc complexes, with purple or red colour being observed in solution. Interesting electrochemical properties were observed, with rare observation of the MnIV/MnIII redox couple. There was observation of oxidation peaks for the pentylthio derivatised Pc with titanium as the central metal; this is unusual since for reported thio derivatives based on TiPc, no oxidation was observed. The vanadium based Pc showed an interesting spectrum for the first ring based reduction. The absorption spectrum obtained for the 1st reduction of the vanadium complex using spectroelectrochemistry would normally indicate a metal based process but comparing with literature it was concluded that it is a ring based reduction process. Generally all the MPc complexes formed a well ordered stable monolayer on the gold electrode. Electrocatalytic studies using L-cysteine revealed that the SAM based on manganese (III) octapentylthio phthalocyanine (AcOMnOPTPc) was the most effective since it catalyses L-cysteine at much lower oxidation potentials and it is also much more stable.
- Full Text:
- Date Issued: 2009
- Authors: Mbambisa, Gcineka
- Date: 2009
- Subjects: Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4368 , http://hdl.handle.net/10962/d1005033 , Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Description: Synthesis of new thio derivatised Pcs with manganese, titanium and vanadium as a central metal is reported. The complexes synthesised were characterised using spectroscopic and electrochemical means. The complexes displayed interesting spectroscopic properties with absorption of the Q band being observed in the near infrared region. These complexes have unusual colours for MPc complexes, with purple or red colour being observed in solution. Interesting electrochemical properties were observed, with rare observation of the MnIV/MnIII redox couple. There was observation of oxidation peaks for the pentylthio derivatised Pc with titanium as the central metal; this is unusual since for reported thio derivatives based on TiPc, no oxidation was observed. The vanadium based Pc showed an interesting spectrum for the first ring based reduction. The absorption spectrum obtained for the 1st reduction of the vanadium complex using spectroelectrochemistry would normally indicate a metal based process but comparing with literature it was concluded that it is a ring based reduction process. Generally all the MPc complexes formed a well ordered stable monolayer on the gold electrode. Electrocatalytic studies using L-cysteine revealed that the SAM based on manganese (III) octapentylthio phthalocyanine (AcOMnOPTPc) was the most effective since it catalyses L-cysteine at much lower oxidation potentials and it is also much more stable.
- Full Text:
- Date Issued: 2009
Synthesis, photophysics and electrochemical study of tin macrocycles
- Authors: Khene, Mielie Samson
- Date: 2008
- Subjects: Electrochemistry , Photochemistry , Phthalocyanines , Macrocyclic compounds , Spectrum analysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4376 , http://hdl.handle.net/10962/d1005041 , Electrochemistry , Photochemistry , Phthalocyanines , Macrocyclic compounds , Spectrum analysis
- Description: Three non-peripherally substituted tin(IV) macrocylic compounds, octahexylphthalocyaninato dichlorotin(IV) (35a), octahexyltetrabenzo-5,10,15-triazaporphyrinato dichlorotin(IV) (35b) and octadecylphthalocyaninato dichlorotin(IV) (35c) were synthesized and their photophysical and electrochemical behaviour studied. Complex (35b), containing a CH group in place of one of the aza nitrogen atom of the phthalocyanine core, shows a split Q band due to its lower symmetry. The triplet state quantum yields were found to be lower than would be expected on the basis of the heavy atom effect of tin as the central metal for phthalocyanine derivatives (35a and 35c). In contrast, (35b) shows a triplet quantum yield ΦT = 0.78. The triplet state lifetimes were solvent dependent, and were higher in THF than in toluene. Cyclic voltammetry and spectroelectrochemistry of the complexes revealed only ring based redox processes. This thesis also reports on the microwave syntheses of tetrasulphonated tin phthalocyanine and tetrasulphonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (< 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The SnTSTBC complex has lower triplet life times and yields, while binding constant and quenching (of bovine serum albumin) constant are lower for SnTSTBC, compared to SnTSPc. Finally Non-peripherally (α) tetra- (40) and octa-(38a) substituted dodecyl-mercapto tin(IV) phthalocyanines where synthesized and the electrochemical behavior studied. Cyclic voltammetry and spectroelectrochemistry show ring-based reductions for (38a) and (40); the former shows two ring oxidations, while the latter shows only one ring based oxidation. The adsorption kinetics of (38a) and (40) on a gold electrode have been investigated by electrochemical impedance spectroscopy (EIS). The equilibrium constant (K) for the adsorption and the Gibbs free energy ΔG(ads) of the self-assembled monolayer (SAMs) were evaluated based on the Frumkin isotherm. The interaction factor between adsorbate –adsorbate molecules is also discussed.
- Full Text:
- Date Issued: 2008
- Authors: Khene, Mielie Samson
- Date: 2008
- Subjects: Electrochemistry , Photochemistry , Phthalocyanines , Macrocyclic compounds , Spectrum analysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4376 , http://hdl.handle.net/10962/d1005041 , Electrochemistry , Photochemistry , Phthalocyanines , Macrocyclic compounds , Spectrum analysis
- Description: Three non-peripherally substituted tin(IV) macrocylic compounds, octahexylphthalocyaninato dichlorotin(IV) (35a), octahexyltetrabenzo-5,10,15-triazaporphyrinato dichlorotin(IV) (35b) and octadecylphthalocyaninato dichlorotin(IV) (35c) were synthesized and their photophysical and electrochemical behaviour studied. Complex (35b), containing a CH group in place of one of the aza nitrogen atom of the phthalocyanine core, shows a split Q band due to its lower symmetry. The triplet state quantum yields were found to be lower than would be expected on the basis of the heavy atom effect of tin as the central metal for phthalocyanine derivatives (35a and 35c). In contrast, (35b) shows a triplet quantum yield ΦT = 0.78. The triplet state lifetimes were solvent dependent, and were higher in THF than in toluene. Cyclic voltammetry and spectroelectrochemistry of the complexes revealed only ring based redox processes. This thesis also reports on the microwave syntheses of tetrasulphonated tin phthalocyanine and tetrasulphonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (< 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The SnTSTBC complex has lower triplet life times and yields, while binding constant and quenching (of bovine serum albumin) constant are lower for SnTSTBC, compared to SnTSPc. Finally Non-peripherally (α) tetra- (40) and octa-(38a) substituted dodecyl-mercapto tin(IV) phthalocyanines where synthesized and the electrochemical behavior studied. Cyclic voltammetry and spectroelectrochemistry show ring-based reductions for (38a) and (40); the former shows two ring oxidations, while the latter shows only one ring based oxidation. The adsorption kinetics of (38a) and (40) on a gold electrode have been investigated by electrochemical impedance spectroscopy (EIS). The equilibrium constant (K) for the adsorption and the Gibbs free energy ΔG(ads) of the self-assembled monolayer (SAMs) were evaluated based on the Frumkin isotherm. The interaction factor between adsorbate –adsorbate molecules is also discussed.
- Full Text:
- Date Issued: 2008
Liquid junction potentials at mixed electrolyte salt bridges
- Authors: Finkelstein, Noel Phillip
- Date: 1957
- Subjects: Hydrogen-ion concentration -- Measurement , Hydrogen-ion concentration , Electrochemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4473 , http://hdl.handle.net/10962/d1011835 , Hydrogen-ion concentration -- Measurement , Hydrogen-ion concentration , Electrochemistry
- Description: The potentiometric method is one of the most exact techniques of electrochemistry. Its use is widespread in both routine measurements, such as pH determination, and in applications which demand the highest accuracy. Perhaps its severest limitation is the error due to liquid junction potentials. Although this has been the subject of much study, and although various means of combating it have been proposed, it has defied all attempts at a satisfactory solution. Indeed, so serious is the position that it has become the accepted practice in the more accurate fields to abandon altogether the use of potentiometric techniques in favour of others, usually less convenient and otherwise less accurate, when the presence of liquid junctions cannot be avoided. Intro. p. 1.
- Full Text:
- Date Issued: 1957
- Authors: Finkelstein, Noel Phillip
- Date: 1957
- Subjects: Hydrogen-ion concentration -- Measurement , Hydrogen-ion concentration , Electrochemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4473 , http://hdl.handle.net/10962/d1011835 , Hydrogen-ion concentration -- Measurement , Hydrogen-ion concentration , Electrochemistry
- Description: The potentiometric method is one of the most exact techniques of electrochemistry. Its use is widespread in both routine measurements, such as pH determination, and in applications which demand the highest accuracy. Perhaps its severest limitation is the error due to liquid junction potentials. Although this has been the subject of much study, and although various means of combating it have been proposed, it has defied all attempts at a satisfactory solution. Indeed, so serious is the position that it has become the accepted practice in the more accurate fields to abandon altogether the use of potentiometric techniques in favour of others, usually less convenient and otherwise less accurate, when the presence of liquid junctions cannot be avoided. Intro. p. 1.
- Full Text:
- Date Issued: 1957