Electroanalysis of thiocyanate using a novel glassy carbon electrode modified by aryl radicals and cobalt tetracarboxyphthalocyanine
- Matemadombo, Fungisai, Westbroek, Philippe, Nyokong, Tebello
- Authors: Matemadombo, Fungisai , Westbroek, Philippe , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268750 , vital:54228 , xlink:href="https://doi.org/10.1016/j.electacta.2007.06.064"
- Description: Electrochemical grafting of 4-nitrobenzenediazonium tetrafluoroborate onto a glassy carbon electrode (GCE) results in the formation of a nitrophenyl radical, which reacts with the surface to form a covalent bond (grafting) and results in a nitrophenyl modified electrode. The nitro group is electrochemically reduced to a NH2 group. Cobalt tetracarboxyphthalocyanine (CoTCPc) complex is then attached to the NH2 group using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) and N-hydroxysuccinimide (NHS) as coupling agents. The new CoTCPc modified electrode was characterized using cyclic voltammetry and then employed for the catalytic oxidation of thiocyanate.
- Full Text:
- Date Issued: 2007
- Authors: Matemadombo, Fungisai , Westbroek, Philippe , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268750 , vital:54228 , xlink:href="https://doi.org/10.1016/j.electacta.2007.06.064"
- Description: Electrochemical grafting of 4-nitrobenzenediazonium tetrafluoroborate onto a glassy carbon electrode (GCE) results in the formation of a nitrophenyl radical, which reacts with the surface to form a covalent bond (grafting) and results in a nitrophenyl modified electrode. The nitro group is electrochemically reduced to a NH2 group. Cobalt tetracarboxyphthalocyanine (CoTCPc) complex is then attached to the NH2 group using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) and N-hydroxysuccinimide (NHS) as coupling agents. The new CoTCPc modified electrode was characterized using cyclic voltammetry and then employed for the catalytic oxidation of thiocyanate.
- Full Text:
- Date Issued: 2007
Immobilization of tetra-amine substituted metallophthalocyanines at gold surfaces modified with mercaptopropionic acid or DTSP-SAMs
- Matemadombo, Fungisai, Westbroek, Philippe, Nyokong, Tebello, Ozoemena, Kenneth, De Clerck, Karen, Kiekens, Paul
- Authors: Matemadombo, Fungisai , Westbroek, Philippe , Nyokong, Tebello , Ozoemena, Kenneth , De Clerck, Karen , Kiekens, Paul
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283924 , vital:56003 , xlink:href="https://doi.org/10.1016/j.electacta.2006.08.027"
- Description: This paper shows that amine substituted cobalt phthalocyanine (CoTAPc) can be deposited on gold surfaces by using an interconnecting layer of a self-assembled monolayer (SAM) of mercaptopropionic acid or Lomant's reagent (dithiobis(N-succinimidyl propionate) (DTSP)). In both cases the new bond formed is obtained by the creation of an amide. The layers were characterized by electrochemistry and showed high coverage fractions (near 100%). Reductive and oxidative desorption of the SAMs limit the useful potential window from −0.6 to +0.5 V versus Ag|AgCl. The SAM-CoTAPc layers show electrocatalytic activities towards oxygen reduction through the Co(I) central metal ion. The amount of CoTAPc molecules deposited (obtained from the Co central metal ion activity in nitrogen purged solutions) revealed that the CoTAPc molecules are bonded in a perpendicular manner at the surface. Taking into account a surface of 200 Å2 for a flatly bonded MPc, this should result in a four times less amount of deposited CoTAPc compared to the experimental value obtained. Both methods showed good results and promising long-term stability and will be interesting tools for further research in surface modification and sensor development.
- Full Text:
- Date Issued: 2007
- Authors: Matemadombo, Fungisai , Westbroek, Philippe , Nyokong, Tebello , Ozoemena, Kenneth , De Clerck, Karen , Kiekens, Paul
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283924 , vital:56003 , xlink:href="https://doi.org/10.1016/j.electacta.2006.08.027"
- Description: This paper shows that amine substituted cobalt phthalocyanine (CoTAPc) can be deposited on gold surfaces by using an interconnecting layer of a self-assembled monolayer (SAM) of mercaptopropionic acid or Lomant's reagent (dithiobis(N-succinimidyl propionate) (DTSP)). In both cases the new bond formed is obtained by the creation of an amide. The layers were characterized by electrochemistry and showed high coverage fractions (near 100%). Reductive and oxidative desorption of the SAMs limit the useful potential window from −0.6 to +0.5 V versus Ag|AgCl. The SAM-CoTAPc layers show electrocatalytic activities towards oxygen reduction through the Co(I) central metal ion. The amount of CoTAPc molecules deposited (obtained from the Co central metal ion activity in nitrogen purged solutions) revealed that the CoTAPc molecules are bonded in a perpendicular manner at the surface. Taking into account a surface of 200 Å2 for a flatly bonded MPc, this should result in a four times less amount of deposited CoTAPc compared to the experimental value obtained. Both methods showed good results and promising long-term stability and will be interesting tools for further research in surface modification and sensor development.
- Full Text:
- Date Issued: 2007
Surface chemistry and electrocatalytic behaviour of tetra-carboxy substituted iron, cobalt and manganese phthalocyanine monolayers on gold electrode
- Mashazi, Philani N, Westbroek, Philippe, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Mashazi, Philani N , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268806 , vital:54233 , xlink:href="https://doi.org/10.1016/j.electacta.2007.08.044"
- Description: Surface chemistry and electrocatalytic properties of self-assembled monolayers of metal tetra-carboxylic acid phthalocyanine complexes with cobalt (Co), iron (Fe) and manganese (Mn) as central metal ions have been studied. These phthalocyanine molecules are immobilized on gold electrode via the coupling reaction between the ring substituents and pre-formed mercaptoethanol self-assembled monolayer (Au-ME SAM). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed chemisorption of mercaptoethanol via sulfur group on gold electrode and also coupling reaction between phthalocyanines and Au-ME SAM. Electrochemical parameters of the immobilized molecules show that these molecules are densely packed with a perpendicular orientation. The potential applications of the gold modified electrodes were investigated towards L-cysteine detection and the analysis at phthalocyanine SAMs. Cobalt and iron tetra-carboxylic acid phthalocyanine monolayers showed good oxidation peak for L-cysteine at potentials where metal oxidation (MIII/MII) takes place and this metal oxidation mediates the catalytic oxidation of L-cysteine. Manganese tetra-carboxylic acid phthalocyanine monolayer also exhibited a good catalytic oxidation peak towards L-cysteine at potentials where MnIV/MnIII redox peak occurs and this redox peak mediates L-cysteine oxidation. The analysis of cysteine at phthalocyanine monolayers displayed good analytical parameters with good detection limits of the orders of 10−7 mol L−1 and good linearity for a studied concentration range up to 60 μmol L−1.
- Full Text:
- Date Issued: 2007
- Authors: Mashazi, Philani N , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268806 , vital:54233 , xlink:href="https://doi.org/10.1016/j.electacta.2007.08.044"
- Description: Surface chemistry and electrocatalytic properties of self-assembled monolayers of metal tetra-carboxylic acid phthalocyanine complexes with cobalt (Co), iron (Fe) and manganese (Mn) as central metal ions have been studied. These phthalocyanine molecules are immobilized on gold electrode via the coupling reaction between the ring substituents and pre-formed mercaptoethanol self-assembled monolayer (Au-ME SAM). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed chemisorption of mercaptoethanol via sulfur group on gold electrode and also coupling reaction between phthalocyanines and Au-ME SAM. Electrochemical parameters of the immobilized molecules show that these molecules are densely packed with a perpendicular orientation. The potential applications of the gold modified electrodes were investigated towards L-cysteine detection and the analysis at phthalocyanine SAMs. Cobalt and iron tetra-carboxylic acid phthalocyanine monolayers showed good oxidation peak for L-cysteine at potentials where metal oxidation (MIII/MII) takes place and this metal oxidation mediates the catalytic oxidation of L-cysteine. Manganese tetra-carboxylic acid phthalocyanine monolayer also exhibited a good catalytic oxidation peak towards L-cysteine at potentials where MnIV/MnIII redox peak occurs and this redox peak mediates L-cysteine oxidation. The analysis of cysteine at phthalocyanine monolayers displayed good analytical parameters with good detection limits of the orders of 10−7 mol L−1 and good linearity for a studied concentration range up to 60 μmol L−1.
- Full Text:
- Date Issued: 2007
Synthesis and electrochemical properties of benzyl-mercapto and dodecyl-mercapto tetrasubstituted manganese phthalocyanine complexes
- Agboola, Bolade, Ozoemena, Kenneth I, Westbroek, Philippe, Nyokong, Tebello
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Westbroek, Philippe , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281321 , vital:55713 , xlink:href="https://doi.org/10.1016/j.electacta.2006.09.002"
- Description: Manganese tetrakis (benzyl-mercapto) phthalocyanine (MnTBMPc) and manganese tetrakis (dodecyl-mercapto) phthalocyanine (MnTDMPc) complexes were synthesized and their spectral and electrochemical properties are reported. Cyclic voltammetric data showed three reversible to quasi-reversible and two irreversible redox processes for both complexes. Ring substituents influenced the positions of both oxidation and reduction redox couples. Spectroelectrochemistry confirmed the first two reductions to be due to MnIIIPc2−/MnIIPc2− and MnIIPc3−/MnIIPc2− processes. The first example of a formation of self-assembled monolayers (SAMs) using thiol substituted MnPc complexes is presented, the SAMs were found to show blocking characteristics towards some faradaic reactions.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Westbroek, Philippe , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281321 , vital:55713 , xlink:href="https://doi.org/10.1016/j.electacta.2006.09.002"
- Description: Manganese tetrakis (benzyl-mercapto) phthalocyanine (MnTBMPc) and manganese tetrakis (dodecyl-mercapto) phthalocyanine (MnTDMPc) complexes were synthesized and their spectral and electrochemical properties are reported. Cyclic voltammetric data showed three reversible to quasi-reversible and two irreversible redox processes for both complexes. Ring substituents influenced the positions of both oxidation and reduction redox couples. Spectroelectrochemistry confirmed the first two reductions to be due to MnIIIPc2−/MnIIPc2− and MnIIPc3−/MnIIPc2− processes. The first example of a formation of self-assembled monolayers (SAMs) using thiol substituted MnPc complexes is presented, the SAMs were found to show blocking characteristics towards some faradaic reactions.
- Full Text:
- Date Issued: 2007
Voltammetric characterisation of the self-assembled monolayers (SAMs) of benzyl-and dodecyl-mercapto tetra substituted metallophthalocyanines complexes
- Agboola, Bolade, Westbroek, Philippe, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Agboola, Bolade , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281414 , vital:55723 , xlink:href="https://doi.org/10.1016/j.elecom.2006.08.047"
- Description: Voltammetric characterisations of cobalt, iron, manganese, nickel and zinc phthalocyanine complexes tetra substituted with benzyl- and dodecyl-mercapto ring substituents and immobilisation on gold electrodes via the self-assembling technique are presented. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, under potential deposition of copper and solution redox chemistry of [Fe(H2O)6 3+ ]/[Fe(H2O)6 2+ ]. The solution chemistry of [Fe(CN)6]−3/[Fe(CN)6]−4 redox process was used to study the orientation of the CoPcs-SAMs and this revealed a possible deviation from flat orientation of the complexes on the gold electrodes when the SAM formation times were greater than 24 h. For SAM formation time at 24 and 48 h, CoTDMPc-SAM showed more inhibition of the [Fe(CN)6]−3/[Fe(CN)6]−4 redox process than the CoTBMPc-SAM counterpart, indicating more blocking characteristics of the dodecylmercapto ring substituents compared to the benzylmercapto counterpart. To avoid SAM desorption, the potential application should be limited to −0.2 to +0.8 V vs. Ag∣AgCl (NaCl, sat’d) in acidic and neutral pH.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281414 , vital:55723 , xlink:href="https://doi.org/10.1016/j.elecom.2006.08.047"
- Description: Voltammetric characterisations of cobalt, iron, manganese, nickel and zinc phthalocyanine complexes tetra substituted with benzyl- and dodecyl-mercapto ring substituents and immobilisation on gold electrodes via the self-assembling technique are presented. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, under potential deposition of copper and solution redox chemistry of [Fe(H2O)6 3+ ]/[Fe(H2O)6 2+ ]. The solution chemistry of [Fe(CN)6]−3/[Fe(CN)6]−4 redox process was used to study the orientation of the CoPcs-SAMs and this revealed a possible deviation from flat orientation of the complexes on the gold electrodes when the SAM formation times were greater than 24 h. For SAM formation time at 24 and 48 h, CoTDMPc-SAM showed more inhibition of the [Fe(CN)6]−3/[Fe(CN)6]−4 redox process than the CoTBMPc-SAM counterpart, indicating more blocking characteristics of the dodecylmercapto ring substituents compared to the benzylmercapto counterpart. To avoid SAM desorption, the potential application should be limited to −0.2 to +0.8 V vs. Ag∣AgCl (NaCl, sat’d) in acidic and neutral pH.
- Full Text:
- Date Issued: 2007
Electrochemical behavior and detection of dopamine and ascorbic acid at an iron (II) tetrasulfophthalocyanine modified carbon paste microelectrode
- Oni, Joshua, Westbroek, Philippe, Nyokong, Tebello
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290279 , vital:56735 , xlink:href="https://doi.org/10.1002/elan.200390104"
- Description: In this article the electrocatalytic behavior of an iron(II)tetrasulfophthalocyanine modified carbon paste microelectrode for the oxidation of dopamine (DA) and ascorbic acid (AA) is described. Although the oxidation potential of ascorbic acid is shifted by over 100 mV to more positive potentials, no peak separation could be obtained. This can be explained by the immediate homogeneous reduction of the oxidation product of dopamine by ascorbic acid in solution. However, this reaction induces a shift of the half-wave potential as a function of ratio of concentration of dopamine to ascorbic acid (cDA/cAA). Therefore it was possible to determine the cAA and cDA from this potential shift and the experimental peak current. Detection limits of 4.5±0.2×10−7 and 7.5±0.5×10−7 mol L−1 were obtained respectively for dopamine and ascorbic acid for cDA/cAA>0.01.
- Full Text:
- Date Issued: 2003
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290279 , vital:56735 , xlink:href="https://doi.org/10.1002/elan.200390104"
- Description: In this article the electrocatalytic behavior of an iron(II)tetrasulfophthalocyanine modified carbon paste microelectrode for the oxidation of dopamine (DA) and ascorbic acid (AA) is described. Although the oxidation potential of ascorbic acid is shifted by over 100 mV to more positive potentials, no peak separation could be obtained. This can be explained by the immediate homogeneous reduction of the oxidation product of dopamine by ascorbic acid in solution. However, this reaction induces a shift of the half-wave potential as a function of ratio of concentration of dopamine to ascorbic acid (cDA/cAA). Therefore it was possible to determine the cAA and cDA from this potential shift and the experimental peak current. Detection limits of 4.5±0.2×10−7 and 7.5±0.5×10−7 mol L−1 were obtained respectively for dopamine and ascorbic acid for cDA/cAA>0.01.
- Full Text:
- Date Issued: 2003
Construction and characterization of carbon paste ultra-microelectrodes
- Oni, Joshua, Westbroek, Philippe, Nyokong, Tebello
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291531 , vital:56884 , xlink:href="https://doi.org/10.1016/S1388-2481(01)00212-0"
- Description: The construction and characterization of carbon paste ultra-microelectrodes is reported. Besides a disc-shaped electrode, a carbon paste band electrode is studied. It was found that for both electrode configurations steady-state currents were obtained but that with the type of electrode material used for the band electrode, the upper limit of ultra-microelectrode dimensions, which could be used was 100–150 μm. Smaller dimensions for the band electrodes resulted in a high resistance due to the limited conductivity of the carbon paste, when using the optimal paste composition. With cyclic voltammetry, the oxidation of [Fe(CN)6]4− was studied at individual constructed electrodes and at ensembles of individual electrodes. Detection limits of less than 10−6moll−1 were obtained. Using the data of the same curves it was possible to test if the electrodes have errors and about 20% of the constructed electrodes did not pass this test. Finally it was found that these electrodes show good stability.
- Full Text:
- Date Issued: 2001
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291531 , vital:56884 , xlink:href="https://doi.org/10.1016/S1388-2481(01)00212-0"
- Description: The construction and characterization of carbon paste ultra-microelectrodes is reported. Besides a disc-shaped electrode, a carbon paste band electrode is studied. It was found that for both electrode configurations steady-state currents were obtained but that with the type of electrode material used for the band electrode, the upper limit of ultra-microelectrode dimensions, which could be used was 100–150 μm. Smaller dimensions for the band electrodes resulted in a high resistance due to the limited conductivity of the carbon paste, when using the optimal paste composition. With cyclic voltammetry, the oxidation of [Fe(CN)6]4− was studied at individual constructed electrodes and at ensembles of individual electrodes. Detection limits of less than 10−6moll−1 were obtained. Using the data of the same curves it was possible to test if the electrodes have errors and about 20% of the constructed electrodes did not pass this test. Finally it was found that these electrodes show good stability.
- Full Text:
- Date Issued: 2001
Photodynamic inactivation of Staphylococcus aureus using low symmetrically substituted phthalocyanines supported on a polystyrene polymer fiber
- Masilela, Nkosiphile, Kleyi, Phumelele, Tshentu, Zenixole, Priniotakis, Georgios, Westbroek, Philippe, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Kleyi, Phumelele , Tshentu, Zenixole , Priniotakis, Georgios , Westbroek, Philippe , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7330 , http://hdl.handle.net/10962/d1020591
- Description: This work reports on the antimicrobial photo-activities of a series of low symmetrically substituted phthalocyanine complexes in solution and in a fiber matrix. Phthalocyanine complexes were successfully electrospun into a polystyrene polymer. The fiber diameter ranged from 240 nm to 390 nm in average. The modified polymer fiber showed successful singlet oxygen production with the Ge monocarboxy phthalocyanine modified fiber giving the highest singlet oxygen quantum yield value of 0.46 due to lack of aggregation when in the polymer. All the unsymmetrically substituted complexes showed antimicrobial activity towards S. Aureus under illumination with visible light. The symmetrical ZnPc and ZnTPCPc showed no activity under illumination with light in the fiber matrix due to low singlet oxygen production. , Original publication is available at http://dx.doi.org/10.1016/j.dyepig.2012.10.001
- Full Text: false
- Authors: Masilela, Nkosiphile , Kleyi, Phumelele , Tshentu, Zenixole , Priniotakis, Georgios , Westbroek, Philippe , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7330 , http://hdl.handle.net/10962/d1020591
- Description: This work reports on the antimicrobial photo-activities of a series of low symmetrically substituted phthalocyanine complexes in solution and in a fiber matrix. Phthalocyanine complexes were successfully electrospun into a polystyrene polymer. The fiber diameter ranged from 240 nm to 390 nm in average. The modified polymer fiber showed successful singlet oxygen production with the Ge monocarboxy phthalocyanine modified fiber giving the highest singlet oxygen quantum yield value of 0.46 due to lack of aggregation when in the polymer. All the unsymmetrically substituted complexes showed antimicrobial activity towards S. Aureus under illumination with visible light. The symmetrical ZnPc and ZnTPCPc showed no activity under illumination with light in the fiber matrix due to low singlet oxygen production. , Original publication is available at http://dx.doi.org/10.1016/j.dyepig.2012.10.001
- Full Text: false
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