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
Comparative electrooxidation of nitrite by electrodeposited Co (II), Fe (II) and Mn (III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines on gold electrodes
- Agboola, Bolade, Nyokong, Tebello
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281212 , vital:55702 , xlink:href="https://doi.org/10.1016/j.aca.2007.01.031"
- Description: This work reports on the electrooxidation of nitrite using Co(II), Fe(II) and Mn(III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines electrodeposited onto a gold electrode. Good catalytic activity (in terms of lowering overpotential) was obtained for these molecules when compared to previously reported MPc catalysts. The catalytic current was found to vary linearly with nitrite concentration in the range employed in this work (0.1–1 mM) and high sensitivities ranging from 6.9 to 9.9 μA mM−1 were observed for all the modified electrodes.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281212 , vital:55702 , xlink:href="https://doi.org/10.1016/j.aca.2007.01.031"
- Description: This work reports on the electrooxidation of nitrite using Co(II), Fe(II) and Mn(III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines electrodeposited onto a gold electrode. Good catalytic activity (in terms of lowering overpotential) was obtained for these molecules when compared to previously reported MPc catalysts. The catalytic current was found to vary linearly with nitrite concentration in the range employed in this work (0.1–1 mM) and high sensitivities ranging from 6.9 to 9.9 μA mM−1 were observed for all the modified electrodes.
- Full Text:
- Date Issued: 2007
Electrocatalytic activity of arylthio tetra-substituted oxotitanium (IV) phthalocyanines towards the oxidation of nitrite
- Tau, Prudence, Nyokong, Tebello
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281234 , vital:55704 , xlink:href="https://doi.org/10.1016/j.electacta.2006.12.059"
- Description: This paper investigates the catalytic activities of arylthio substituted oxotitanium phthalocyanine (OTiPc) complexes that are immobilized on the glassy carbon electrode by electropolymerization, towards the oxidation of nitrite. The complexes are peripherally and non-peripherally substituted with phenylthio and benzylthio groups, namely 1a, 1b, 2a and 2b. All the modified electrodes exhibited improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a two-electron mechanism producing nitrate ions. Catalytic currents are enhanced and nitrite overpotential reduced to ∼0.60 V. Kinetic parameters are determined for all complexes and a mechanism is proposed.
- Full Text:
- Date Issued: 2007
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281234 , vital:55704 , xlink:href="https://doi.org/10.1016/j.electacta.2006.12.059"
- Description: This paper investigates the catalytic activities of arylthio substituted oxotitanium phthalocyanine (OTiPc) complexes that are immobilized on the glassy carbon electrode by electropolymerization, towards the oxidation of nitrite. The complexes are peripherally and non-peripherally substituted with phenylthio and benzylthio groups, namely 1a, 1b, 2a and 2b. All the modified electrodes exhibited improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a two-electron mechanism producing nitrate ions. Catalytic currents are enhanced and nitrite overpotential reduced to ∼0.60 V. Kinetic parameters are determined for all complexes and a mechanism is proposed.
- Full Text:
- Date Issued: 2007
Tuning the redox properties of metalloporphyrin-and metallophthalocyanine-based molecular electrodes for the highest electrocatalytic activity in the oxidation of thiols
- Bedioui, Fethi, Griveau, Sophie, Nyokong, Tebello, Appleby, A John, Caro, Claudia A, Gulppi, Miguel, Ochoa, Gonzalo, Zagal, José H
- Authors: Bedioui, Fethi , Griveau, Sophie , Nyokong, Tebello , Appleby, A John , Caro, Claudia A , Gulppi, Miguel , Ochoa, Gonzalo , Zagal, José H
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283988 , vital:56009 , xlink:href="https://doi.org/10.1039/B618767F"
- Description: In this work we discuss different approaches for achieving electrodes modified with N4 macrocyclic complexes for the catalysis of the electrochemical oxidation of thiols. These approaches involve adsorption, electropolymerization and molecular anchoring using self assembled monolayers. We also discuss the parameters that determine the reactivity of these complexes. Catalytic activity is associated with the nature of the central metal, redox potentials and Hammett parameters of substituents on the ligand. Correlations between catalytic activity (log i at constant E) and the redox potential of catalysts for complexes of Cr, Mn, Fe, Co, Ni and Cu are linear with an increase of activity for more positive redox potentials. For a great variety complexes bearing the same metal center (Co) correlations between log i and Eo′ of the Co(II)/Co(I) couple have the shape of an unsymmetric volcano. This indicates that the potential of the Co(II)/Co(I) couple can be tuned using the appropiate ligand to achieve maximum catalytic activity. Maximum activity probably corresponds to a ΔG of adsorption of the thiol on the Co center equal to zero, and to a coverage of active sites by the thiol equal to 0.5.
- Full Text:
- Date Issued: 2007
- Authors: Bedioui, Fethi , Griveau, Sophie , Nyokong, Tebello , Appleby, A John , Caro, Claudia A , Gulppi, Miguel , Ochoa, Gonzalo , Zagal, José H
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283988 , vital:56009 , xlink:href="https://doi.org/10.1039/B618767F"
- Description: In this work we discuss different approaches for achieving electrodes modified with N4 macrocyclic complexes for the catalysis of the electrochemical oxidation of thiols. These approaches involve adsorption, electropolymerization and molecular anchoring using self assembled monolayers. We also discuss the parameters that determine the reactivity of these complexes. Catalytic activity is associated with the nature of the central metal, redox potentials and Hammett parameters of substituents on the ligand. Correlations between catalytic activity (log i at constant E) and the redox potential of catalysts for complexes of Cr, Mn, Fe, Co, Ni and Cu are linear with an increase of activity for more positive redox potentials. For a great variety complexes bearing the same metal center (Co) correlations between log i and Eo′ of the Co(II)/Co(I) couple have the shape of an unsymmetric volcano. This indicates that the potential of the Co(II)/Co(I) couple can be tuned using the appropiate ligand to achieve maximum catalytic activity. Maximum activity probably corresponds to a ΔG of adsorption of the thiol on the Co center equal to zero, and to a coverage of active sites by the thiol equal to 0.5.
- Full Text:
- Date Issued: 2007
Factors affecting ethical judgement of South African chartered accountants
- Maree, Kevin W, Radloff, Sarah E
- Authors: Maree, Kevin W , Radloff, Sarah E
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: Article
- Identifier: vital:6073 , http://hdl.handle.net/10962/d1001647 , ISSN 1022-2529 , http://0-dx.doi.org.wam.seals.ac.za/10.1108/10222529200700001
- Description: The start of the twenty-first century was marred by a spate of company collapses that involved fraudulent accounting activity. In many cases, company executives, many of whom belonged to the accounting profession, perpetrated the fraud. As a result, internationally, the accounting profession has suffered an enormous loss of goodwill, and its reputation as a profession with integrity has been severely harmed. Accounting professionals are no longer accorded the high regard they commanded in the past. The consequences for the profession have been far-reaching: accounting now faces a long, uphill battle to restore its reputation and to regain the trust of the international business community. This study replicates two famous international studies in the South African context. The focus of the study was to establish whether factors such as the Code of Professional Conduct of the South African Institute of Chartered Accountants (SAICA), the corporate ethical environment and their age influence the ethical judgement of individual accountants. The first such study was conducted in the United States of America (USA), and it was followed by similar research in Turkey. The results of these two studies suggested very different factors that could influence accountants' ethical judgement. The study reported in this article investigated South African chartered accountants; and its results were similar to those obtained in the US study.
- Full Text:
- Date Issued: 2007
- Authors: Maree, Kevin W , Radloff, Sarah E
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: Article
- Identifier: vital:6073 , http://hdl.handle.net/10962/d1001647 , ISSN 1022-2529 , http://0-dx.doi.org.wam.seals.ac.za/10.1108/10222529200700001
- Description: The start of the twenty-first century was marred by a spate of company collapses that involved fraudulent accounting activity. In many cases, company executives, many of whom belonged to the accounting profession, perpetrated the fraud. As a result, internationally, the accounting profession has suffered an enormous loss of goodwill, and its reputation as a profession with integrity has been severely harmed. Accounting professionals are no longer accorded the high regard they commanded in the past. The consequences for the profession have been far-reaching: accounting now faces a long, uphill battle to restore its reputation and to regain the trust of the international business community. This study replicates two famous international studies in the South African context. The focus of the study was to establish whether factors such as the Code of Professional Conduct of the South African Institute of Chartered Accountants (SAICA), the corporate ethical environment and their age influence the ethical judgement of individual accountants. The first such study was conducted in the United States of America (USA), and it was followed by similar research in Turkey. The results of these two studies suggested very different factors that could influence accountants' ethical judgement. The study reported in this article investigated South African chartered accountants; and its results were similar to those obtained in the US study.
- Full Text:
- Date Issued: 2007
The effects of fire on post-fire seed germination of selected Savanna woody species
- Authors: Shackleton, Charlie M
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/183104 , vital:43912 , xlink:href=" https://doi.org/10.1111/j.1365-2028.2007.00766.x"
- Description: Although fire is recognized as an integral component of savanna dynamics, there is a dearth of understanding of its impacts on woody plant seeds. This study examined the impacts of fire in stimulating or constraining post-fire germination of seven common savanna woody species. Seeds of two species (Combretum hereroense and Euclea natalensis) failed to germinate irrespective of fire treatment. For the remaining five species, fire effects were dependent on seed location as either on the soil surface or buried. For surface seeds, fire effects reduced germination in four of the species, and stimulated it for one species (Acacia swazica). For buried seeds, fire had no effect. A significant proportion of surface seeds were destroyed by fire, and overall germination was higher for buried seed for most species other than A. swazica.
- Full Text:
- Date Issued: 2007
- Authors: Shackleton, Charlie M
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/183104 , vital:43912 , xlink:href=" https://doi.org/10.1111/j.1365-2028.2007.00766.x"
- Description: Although fire is recognized as an integral component of savanna dynamics, there is a dearth of understanding of its impacts on woody plant seeds. This study examined the impacts of fire in stimulating or constraining post-fire germination of seven common savanna woody species. Seeds of two species (Combretum hereroense and Euclea natalensis) failed to germinate irrespective of fire treatment. For the remaining five species, fire effects were dependent on seed location as either on the soil surface or buried. For surface seeds, fire effects reduced germination in four of the species, and stimulated it for one species (Acacia swazica). For buried seeds, fire had no effect. A significant proportion of surface seeds were destroyed by fire, and overall germination was higher for buried seed for most species other than A. swazica.
- Full Text:
- Date Issued: 2007
Excited state dynamics of zinc and aluminum phthalocyanine carboxylates
- Idowu, Mopelola, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271228 , vital:54523 , xlink:href="https://doi.org/10.1016/j.saa.2007.01.025"
- Description: Photophysical parameters for zinc and aluminium tetracarboxylphthalocyanines (ZnTCPc and AlTCPc, respectively) and their octacarboxy substituted counterparts (ZnOCPc and AlOCPc) were studied. Data for the fluorescence quenching of the complexes by benzoquinone (BQ) were treated using the Stern–Volmer analysis, and the quenching was found to follow a diffusion-controlled (dynamic) bimolecular mechanism. Theoretical values of bimolecular rate constant for complex-BQ interactions were determined using the Stokes–Einstein–Smoluchowski model; and the values, together with the Stern–Volmer quenching constants were used in calculating the fluorescence lifetimes of the complexes. The thermodynamics of the MPc-BQ interaction, in terms of solvent reorientation energy is also discussed.
- Full Text:
- Date Issued: 2007
- Authors: Idowu, Mopelola , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271228 , vital:54523 , xlink:href="https://doi.org/10.1016/j.saa.2007.01.025"
- Description: Photophysical parameters for zinc and aluminium tetracarboxylphthalocyanines (ZnTCPc and AlTCPc, respectively) and their octacarboxy substituted counterparts (ZnOCPc and AlOCPc) were studied. Data for the fluorescence quenching of the complexes by benzoquinone (BQ) were treated using the Stern–Volmer analysis, and the quenching was found to follow a diffusion-controlled (dynamic) bimolecular mechanism. Theoretical values of bimolecular rate constant for complex-BQ interactions were determined using the Stokes–Einstein–Smoluchowski model; and the values, together with the Stern–Volmer quenching constants were used in calculating the fluorescence lifetimes of the complexes. The thermodynamics of the MPc-BQ interaction, in terms of solvent reorientation energy is also discussed.
- Full Text:
- Date Issued: 2007
Photophysical and photochemical properties of zinc and aluminum phthalocyanines in the presence of magnetic fluid
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281298 , vital:55710 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.12.013"
- Description: The effect of magnetic fluid (MF) on the photophysical and photochemical parameters of zinc and aluminum phthalocyanines are reported. The complexes studied are zinc (II) phthalocyanine (ZnPc), chloroaluminum phthalocyanine ((Cl)AlPc) and tetrasulfonated aluminum phthalocyanine ((Cl)AlTSPc). The parameters are studied in dimethylsulfoxide (DMSO) for all complexes and also in aqueous media for (Cl)AlTSPc. The triplet lifetimes for (Cl)AlTSPc and ZnPc decreased while the triplet quantum yields increased in the presence of MF. For (Cl)AlPc, the triplet lifetimes were found to increase with decrease in laser energy while there was photoreduction to the Pc−3 species. Singlet oxygen and photodegradation quantum yields decreased in the presence of MF, suggesting quenching.
- Full Text:
- Date Issued: 2007
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281298 , vital:55710 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.12.013"
- Description: The effect of magnetic fluid (MF) on the photophysical and photochemical parameters of zinc and aluminum phthalocyanines are reported. The complexes studied are zinc (II) phthalocyanine (ZnPc), chloroaluminum phthalocyanine ((Cl)AlPc) and tetrasulfonated aluminum phthalocyanine ((Cl)AlTSPc). The parameters are studied in dimethylsulfoxide (DMSO) for all complexes and also in aqueous media for (Cl)AlTSPc. The triplet lifetimes for (Cl)AlTSPc and ZnPc decreased while the triplet quantum yields increased in the presence of MF. For (Cl)AlPc, the triplet lifetimes were found to increase with decrease in laser energy while there was photoreduction to the Pc−3 species. Singlet oxygen and photodegradation quantum yields decreased in the presence of MF, suggesting quenching.
- Full Text:
- Date Issued: 2007
Comparative photocatalytic efficiency of oxotitanium (IV) phthalocyanines for the oxidation of 1-hexene
- Tau, Prudence, Nyokong, Tebello
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271193 , vital:54520 , xlink:href="https://doi.org/10.1016/j.molcata.2007.04.005"
- Description: The comparative photocatalytic activities of aryloxy and arylthio tetrasubstituted oxotitanium(IV) phthalocyanine complexes for the oxidation of 1-hexene in DCM are reported for the first time. The singlet oxygen quantum yield, photostability and photocatalytic properties are investigated. The catalysts effectively catalyse 1-hexene to 1,2-epoxyhexane and 1-hexen-3-ol as major and minor products respectively. The photooxidation products are formed via two reaction mechanisms, namely via singlet oxygen (Type II) and radical (Type I) reaction pathways. These are also dependent on the singlet oxygen quantum yields and photostabilities of the phthalocyanines. Complex 1a that is peripherally substituted with phenoxy groups exhibited the best activity in terms of overall performance.
- Full Text:
- Date Issued: 2007
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271193 , vital:54520 , xlink:href="https://doi.org/10.1016/j.molcata.2007.04.005"
- Description: The comparative photocatalytic activities of aryloxy and arylthio tetrasubstituted oxotitanium(IV) phthalocyanine complexes for the oxidation of 1-hexene in DCM are reported for the first time. The singlet oxygen quantum yield, photostability and photocatalytic properties are investigated. The catalysts effectively catalyse 1-hexene to 1,2-epoxyhexane and 1-hexen-3-ol as major and minor products respectively. The photooxidation products are formed via two reaction mechanisms, namely via singlet oxygen (Type II) and radical (Type I) reaction pathways. These are also dependent on the singlet oxygen quantum yields and photostabilities of the phthalocyanines. Complex 1a that is peripherally substituted with phenoxy groups exhibited the best activity in terms of overall performance.
- Full Text:
- Date Issued: 2007
Photophysical and photochemical studies of long chain-substituted zinc phthalocyanines
- Durmus, Mahmut, Ahsen, Vefa, Nyokong, Tebello
- Authors: Durmus, Mahmut , Ahsen, Vefa , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281310 , vital:55711 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.08.025"
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetra(13,17-dioxanonacosane-15-hydroxy)-substituted zinc phthalocyanines (1, 2). General trends are described for quantum yields of photodegradation, fluorescence yields, triplet lifetimes and triplet quantum yields as well as singlet quantum yields of these compounds in dimethylformamide (DMF) and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2) are reported.
- Full Text:
- Date Issued: 2007
- Authors: Durmus, Mahmut , Ahsen, Vefa , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281310 , vital:55711 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.08.025"
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetra(13,17-dioxanonacosane-15-hydroxy)-substituted zinc phthalocyanines (1, 2). General trends are described for quantum yields of photodegradation, fluorescence yields, triplet lifetimes and triplet quantum yields as well as singlet quantum yields of these compounds in dimethylformamide (DMF) and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2) are reported.
- Full Text:
- Date Issued: 2007
Cobalt Phthalocyanine Molecular Electrode for the Electrochemical Investigation of the Release of Glutathione upon Copper-Catalyzed Decomposition of S-Nitrosoglutathione
- Sehlotho, Nthapo, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281201 , vital:55701 , xlink:href="https://doi.org/10.1002/elan.200603656"
- Description: Decomposition of S-nitrosoglutathione (GSNO) in phosphate buffer solution at physiological pH 7.4 in the presence of cuprous ion as a catalyst and sodium borohydride as a reducing agent is analyzed by observing the transient apparition of reduced glutathione GSH through its electrooxidation. Transient formation of GSH, upon decomposition of 1 mM GSNO in presence of 0.025 mM Cu(NO3)2 and 1 mM NaBH4 was detected by using an ordinary pyrolytic graphite electrode modified with an adsorbed monolayer of cobalt phthalocyanine at 0 V vs. SCE.
- Full Text:
- Date Issued: 2007
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281201 , vital:55701 , xlink:href="https://doi.org/10.1002/elan.200603656"
- Description: Decomposition of S-nitrosoglutathione (GSNO) in phosphate buffer solution at physiological pH 7.4 in the presence of cuprous ion as a catalyst and sodium borohydride as a reducing agent is analyzed by observing the transient apparition of reduced glutathione GSH through its electrooxidation. Transient formation of GSH, upon decomposition of 1 mM GSNO in presence of 0.025 mM Cu(NO3)2 and 1 mM NaBH4 was detected by using an ordinary pyrolytic graphite electrode modified with an adsorbed monolayer of cobalt phthalocyanine at 0 V vs. SCE.
- Full Text:
- Date Issued: 2007
Realistic idealism
- Authors: Tabensky, Pedro
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/305700 , vital:58605 , xlink:href="https://doi.org/10.3167/th.2007.5411306"
- Description: Realists found in International Relations (IR) circles explicitly assign relatively minor importance to ethical ideals in their analyses of the international political domain, although a robust ethical ideal of sorts, implicitly for the most part qua ethical ideal, does guide their analysis of the international arena. For them, the key to order in the international arena is the balance of power reached between different nations aiming at asserting their wills, promoting their interests, in what is in effect perceived by IR realists as an international battle of wills guided primarily by the logic of power. As a purely descriptive claim regarding how nations, for the most part, actually behave, I have no axe to grind with the IR realist, or at least I do not have to grind an axe with them on this matter for the purposes of this paper, but the IR realist is committed to more than merely describing the behaviour of the international order. IR realists, implicitly and paradoxically, are forced, by the logic of their own position, to believe that the ethical ideal that ought to be guiding the international order is the balance of power between competing interests guiding the international behaviour of nations in their quest for power and (alleged) survival. The primary moral dictum of their position is that nations ought to pursue their self-interested interests relentlessly, but only to the extent that the fragile balance of power is not upset (which is, at any rate, a central ingredient for promoting national self-interest). IR realists do not altogether explicitly deny the role of ideals, but the role they assign to ideals is limited and, I will argue, ultimately incoherent, for ideals ought to be understood as flowing from the structure of our embodied existences and into every nook and cranny of our lives, understood individually and collectively, nationally and internationally. We are active creatures, as Aristotle observed, and activities are defined as such in relation to a functional ideal, an ideal of operation, which flows from our specific modes of embodiment. The norms or ends guiding the international political order ought to flow from this understanding of the human subject ideally conceived, as opposed to the largely Machiavellian pessimistic understanding of the human situation informing IR realism; a pessimism that stems from the fallacious move from raw observation to normative recommendation. To claim that our ends are Machiavellian, we shall see, is incoherent and this incoherence is at the heart of IR realism. The demands of reason, we shall see, should push us in the direction of a particular variety of optimism. By using a broadly Aristotelian teleological technique of analysis I will show that IR realists cannot be right. Without placing ideals at the centre of our understandings of our political lives we would be unable properly to understand the political domain, including the specific sphere of concern of IR specialists. The purely observational descriptions alluded to above do not provide the grounds for proper understanding. What does provide a proper understanding, we shall see, is observation through a conceptual lens informed by a teleological understanding of the human person (observation in the light of a conception of the good). That I think a robust conception of the good, of the set of ideals that out to be guiding rational human life, is necessary for properly understanding the international arena does not of course mean that I advocate any such conception of the good. As claimed above, the sort that I advocate, following Aristotle’s footsteps, flows from the specific configuration of our embodied lives. I refer to this form of idealism as realistic idealism.
- Full Text:
- Date Issued: 2007
- Authors: Tabensky, Pedro
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/305700 , vital:58605 , xlink:href="https://doi.org/10.3167/th.2007.5411306"
- Description: Realists found in International Relations (IR) circles explicitly assign relatively minor importance to ethical ideals in their analyses of the international political domain, although a robust ethical ideal of sorts, implicitly for the most part qua ethical ideal, does guide their analysis of the international arena. For them, the key to order in the international arena is the balance of power reached between different nations aiming at asserting their wills, promoting their interests, in what is in effect perceived by IR realists as an international battle of wills guided primarily by the logic of power. As a purely descriptive claim regarding how nations, for the most part, actually behave, I have no axe to grind with the IR realist, or at least I do not have to grind an axe with them on this matter for the purposes of this paper, but the IR realist is committed to more than merely describing the behaviour of the international order. IR realists, implicitly and paradoxically, are forced, by the logic of their own position, to believe that the ethical ideal that ought to be guiding the international order is the balance of power between competing interests guiding the international behaviour of nations in their quest for power and (alleged) survival. The primary moral dictum of their position is that nations ought to pursue their self-interested interests relentlessly, but only to the extent that the fragile balance of power is not upset (which is, at any rate, a central ingredient for promoting national self-interest). IR realists do not altogether explicitly deny the role of ideals, but the role they assign to ideals is limited and, I will argue, ultimately incoherent, for ideals ought to be understood as flowing from the structure of our embodied existences and into every nook and cranny of our lives, understood individually and collectively, nationally and internationally. We are active creatures, as Aristotle observed, and activities are defined as such in relation to a functional ideal, an ideal of operation, which flows from our specific modes of embodiment. The norms or ends guiding the international political order ought to flow from this understanding of the human subject ideally conceived, as opposed to the largely Machiavellian pessimistic understanding of the human situation informing IR realism; a pessimism that stems from the fallacious move from raw observation to normative recommendation. To claim that our ends are Machiavellian, we shall see, is incoherent and this incoherence is at the heart of IR realism. The demands of reason, we shall see, should push us in the direction of a particular variety of optimism. By using a broadly Aristotelian teleological technique of analysis I will show that IR realists cannot be right. Without placing ideals at the centre of our understandings of our political lives we would be unable properly to understand the political domain, including the specific sphere of concern of IR specialists. The purely observational descriptions alluded to above do not provide the grounds for proper understanding. What does provide a proper understanding, we shall see, is observation through a conceptual lens informed by a teleological understanding of the human person (observation in the light of a conception of the good). That I think a robust conception of the good, of the set of ideals that out to be guiding rational human life, is necessary for properly understanding the international arena does not of course mean that I advocate any such conception of the good. As claimed above, the sort that I advocate, following Aristotle’s footsteps, flows from the specific configuration of our embodied lives. I refer to this form of idealism as realistic idealism.
- Full Text:
- Date Issued: 2007
Synthesis and solvent effects on the electronic absorption and fluorescence spectral properties of substituted zinc phthalocyanines
- Durmus, Mahmut, Nyokong, Tebello
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293279 , vital:57071 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.018"
- Description: The synthesis and spectroscopic properties of the following tetra- and octa-substituted aryloxy zinc(II) phthalocyanines are reported for the first time: 1,(4)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (7); 2,(3)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (8); 2,3-(octabenzyloxyphenoxyphthalocyaninato) zinc(II) (9). The new compounds have been characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. Spectroscopic properties of these compounds were investigated in different solvents. Protonation of non-peripherally substituted complex 7 resulted in the splitting and red-shifting of the Q-band. The peripherally substituted derivatives 8 and 9, did not show the split in the Q-band. Fluorescence spectra of the derivatives show Stokes shifts typical of MPc complexes.
- Full Text:
- Date Issued: 2007
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293279 , vital:57071 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.018"
- Description: The synthesis and spectroscopic properties of the following tetra- and octa-substituted aryloxy zinc(II) phthalocyanines are reported for the first time: 1,(4)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (7); 2,(3)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (8); 2,3-(octabenzyloxyphenoxyphthalocyaninato) zinc(II) (9). The new compounds have been characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. Spectroscopic properties of these compounds were investigated in different solvents. Protonation of non-peripherally substituted complex 7 resulted in the splitting and red-shifting of the Q-band. The peripherally substituted derivatives 8 and 9, did not show the split in the Q-band. Fluorescence spectra of the derivatives show Stokes shifts typical of MPc complexes.
- Full Text:
- Date Issued: 2007
Microwave synthesis and photophysics of new tetrasulfonated tin (II) macrocycles
- Khene, Samson, Ogunsipe, Abimbola, Antunes, Edith M, Nyokong, Tebello
- Authors: Khene, Samson , Ogunsipe, Abimbola , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281269 , vital:55708 , xlink:href="https://doi.org/10.1142/S108842460700014X"
- Description: This work reports on the microwave synthesis of tetrasulfonated tin phthalocyanine and tetrasulfonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (more than 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 α,β,γ-tetrabenzcorrole complex has lower triplet life times and yields, while the binding constant and quenching (of bovine serum albumin) constant are lower for α,β,γ-tetrabenzcorrole compared to tetrasulfonated tin phthalocyanine.
- Full Text:
- Date Issued: 2007
- Authors: Khene, Samson , Ogunsipe, Abimbola , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281269 , vital:55708 , xlink:href="https://doi.org/10.1142/S108842460700014X"
- Description: This work reports on the microwave synthesis of tetrasulfonated tin phthalocyanine and tetrasulfonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (more than 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 α,β,γ-tetrabenzcorrole complex has lower triplet life times and yields, while the binding constant and quenching (of bovine serum albumin) constant are lower for α,β,γ-tetrabenzcorrole compared to tetrasulfonated tin phthalocyanine.
- Full Text:
- Date Issued: 2007
Photophysical, photochemical and bovine serum albumin binding studies on water-soluble gallium (III) phthalocyanine derivatives
- Ogunsipe, Abimbola, Nyokong, Tebello, Durmus, Mahmut
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello , Durmus, Mahmut
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271239 , vital:54524 , xlink:href="https://doi.org/10.1142/S1088424607000746"
- Description: Spectral, photophysical, photochemical and bovine serum albumin binding studies on some gallium(III) derivatives - {1,(4)-(tetrapyridyloxyphthalocyaninato)gallium(III), (αGaPc); 2,(3)-(tetrapyridyloxyphthalocyaninato)gallium(III), (βGaPc); and their quaternized derivatives: QαGaPc and QβGaPc)} are hereby presented. β-Substituted complexes are more fluorescent, but show lower tendencies to undergo intersystem crossing than the α-substituted, as judged by their fluorescence and triplet quantum yield values. The quaternized derivatives (QGaPc) are water-soluble and non-aggregated, which makes them potential photosensitizers of choice for photodynamic therapy applications; these amphiphilic compounds also bind strongly to bovine serum albumin in 1:1 stoichiometries, and with binding constants (Kb) in the order of 106 M−1.
- Full Text:
- Date Issued: 2007
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello , Durmus, Mahmut
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271239 , vital:54524 , xlink:href="https://doi.org/10.1142/S1088424607000746"
- Description: Spectral, photophysical, photochemical and bovine serum albumin binding studies on some gallium(III) derivatives - {1,(4)-(tetrapyridyloxyphthalocyaninato)gallium(III), (αGaPc); 2,(3)-(tetrapyridyloxyphthalocyaninato)gallium(III), (βGaPc); and their quaternized derivatives: QαGaPc and QβGaPc)} are hereby presented. β-Substituted complexes are more fluorescent, but show lower tendencies to undergo intersystem crossing than the α-substituted, as judged by their fluorescence and triplet quantum yield values. The quaternized derivatives (QGaPc) are water-soluble and non-aggregated, which makes them potential photosensitizers of choice for photodynamic therapy applications; these amphiphilic compounds also bind strongly to bovine serum albumin in 1:1 stoichiometries, and with binding constants (Kb) in the order of 106 M−1.
- Full Text:
- Date Issued: 2007
Thiol oxidation at 2-mercaptopyrimidine-appended cobalt phthalocyanine modified glassy carbon electrodes
- Obirai, Joseph C, Nyokong, Tebello
- Authors: Obirai, Joseph C , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281403 , vital:55722 , xlink:href="https://doi.org/10.1016/j.jelechem.2006.10.033"
- Description: The electrocatalytic activity of cobalt tetra-2-mercaptopyrimidylphthalocyanine-modified glassy carbon electrode (CoTMPyrPc-GCE) toward gluthathione, L-cysteine and 2-mercaptoethanol has been investigated. CoTMPyrPc-GCE provides a significant improvement on the reported oxidation potential of L-cysteine in pH 4.0 phosphate buffered solution. The oxidation peak potential (Ep), for L-cysteine, was 0.15 V – a relatively lowered oxidation potential compared to reported phthalocyanine complexes. The electrode prepared by drop-dry/thermal annealing method was very stable and sensitive over a long period of time. The stability has been attributed to the thermal annealing and the structure of the mercaptopyrimidine on the periphery of the CoPc.
- Full Text:
- Date Issued: 2007
- Authors: Obirai, Joseph C , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281403 , vital:55722 , xlink:href="https://doi.org/10.1016/j.jelechem.2006.10.033"
- Description: The electrocatalytic activity of cobalt tetra-2-mercaptopyrimidylphthalocyanine-modified glassy carbon electrode (CoTMPyrPc-GCE) toward gluthathione, L-cysteine and 2-mercaptoethanol has been investigated. CoTMPyrPc-GCE provides a significant improvement on the reported oxidation potential of L-cysteine in pH 4.0 phosphate buffered solution. The oxidation peak potential (Ep), for L-cysteine, was 0.15 V – a relatively lowered oxidation potential compared to reported phthalocyanine complexes. The electrode prepared by drop-dry/thermal annealing method was very stable and sensitive over a long period of time. The stability has been attributed to the thermal annealing and the structure of the mercaptopyrimidine on the periphery of the CoPc.
- 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
Novel gallium (III) phthalocyanine derivatives–Synthesis, photophysics and photochemistry
- Chauke, Vongani, Ogunsipe, Abimbola, Durmus, Mahmut, Nyokong, Tebello
- Authors: Chauke, Vongani , Ogunsipe, Abimbola , Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283118 , vital:55912 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.016"
- Description: The syntheses of gallium(III) chloride phthalocyanine {(Cl)GaPc}, octaphenoxyphthalocyaninato gallium(III) chloride {(Cl)GaOPPc} and octakis(4-tert-butylphenoxy)phthalocyaninato gallium(III) chloride {(Cl)GaOTBPPc}; as well as their photophysical and photochemical parameters are hereby presented. Fluorescence quantum yields do not vary much among the three metallophthalocyanines (MPcs); therefore it was concluded that the effect of the substituents is not significant amongst (Cl)GaPc, (Cl)GaOPPc and (Cl)GaOTBPPc. Solvents effects, however, had an effect on the results. Triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. We have also reported photodegradation and singlet oxygen quantum yields. There was no clear correlation between the later parameters. It was, however, established that the three MPcs were stable.
- Full Text:
- Date Issued: 2007
- Authors: Chauke, Vongani , Ogunsipe, Abimbola , Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283118 , vital:55912 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.016"
- Description: The syntheses of gallium(III) chloride phthalocyanine {(Cl)GaPc}, octaphenoxyphthalocyaninato gallium(III) chloride {(Cl)GaOPPc} and octakis(4-tert-butylphenoxy)phthalocyaninato gallium(III) chloride {(Cl)GaOTBPPc}; as well as their photophysical and photochemical parameters are hereby presented. Fluorescence quantum yields do not vary much among the three metallophthalocyanines (MPcs); therefore it was concluded that the effect of the substituents is not significant amongst (Cl)GaPc, (Cl)GaOPPc and (Cl)GaOTBPPc. Solvents effects, however, had an effect on the results. Triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. We have also reported photodegradation and singlet oxygen quantum yields. There was no clear correlation between the later parameters. It was, however, established that the three MPcs were stable.
- Full Text:
- Date Issued: 2007
Critical assessment of the quartz crystal microbalance with dissipation as an analytical tool for biosensor development and fundamental studies
- Fogel, Ronen, Mashazi, Philani N, Nyokong, Tebello, Limson, Janice
- Authors: Fogel, Ronen , Mashazi, Philani N , Nyokong, Tebello , Limson, Janice
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271204 , vital:54521 , xlink:href="https://doi.org/10.1016/j.bios.2007.03.012"
- Description: One of the challenges in electrochemical biosensor design is gaining a fundamental knowledge of the processes underlying immobilisation of the molecules onto the electrode surface. This is of particular importance in biocomposite sensors where concerns have arisen as to the nature of the interaction between the biological and synthetic molecules immobilised. We examined the use of the Quartz Crystal Microbalance with Dissipation (QCM-D) as a tool for fundamental analyses of a model sensor constructed by the immobilisation of cobalt(II) phthalocyanine (TCACoPc) and glucose oxidase (GOx) onto a gold-quartz electrode (electrode surface) for the enhanced detection of glucose. The model sensor was constructed in aqueous phase and covalently linked the gold surface to the TCACoPc, and the TCACoPc to the GOx, using the QCM-D. The aqueous metallophthalocyanine (MPc) formed a multi-layer over the surface of the electrode, which could be removed to leave a monolayer with a mass loading that compared favourably to the theoretical value expected. Analysis of frequency and dissipation plots indicated covalent attachment of glucose oxidase onto the metallophthalocyanine layer. The amount of GOx bound using the model system compared favourably to calculations derived from the maximal amperometric functioning of the electrochemical sensor (examined in previously-published literature, Mashazi, P.N., Ozoemena, K.I., Nyokong, T., 2006. Electrochim. Acta 52, 177–186), but not to theoretical values derived from dimensions of GOx as established by crystallography. The strength of the binding of the GOx film with the TCACoPc layer was tested by using 2% SDS as a denaturant/surfactant, and the GOx film was not found to be significantly affected by exposure to this. This paper thus showed that QCM-D can be used in order to model essential processes and interactions that dictate the functional parameters of a biosensor.
- Full Text:
- Date Issued: 2007
- Authors: Fogel, Ronen , Mashazi, Philani N , Nyokong, Tebello , Limson, Janice
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271204 , vital:54521 , xlink:href="https://doi.org/10.1016/j.bios.2007.03.012"
- Description: One of the challenges in electrochemical biosensor design is gaining a fundamental knowledge of the processes underlying immobilisation of the molecules onto the electrode surface. This is of particular importance in biocomposite sensors where concerns have arisen as to the nature of the interaction between the biological and synthetic molecules immobilised. We examined the use of the Quartz Crystal Microbalance with Dissipation (QCM-D) as a tool for fundamental analyses of a model sensor constructed by the immobilisation of cobalt(II) phthalocyanine (TCACoPc) and glucose oxidase (GOx) onto a gold-quartz electrode (electrode surface) for the enhanced detection of glucose. The model sensor was constructed in aqueous phase and covalently linked the gold surface to the TCACoPc, and the TCACoPc to the GOx, using the QCM-D. The aqueous metallophthalocyanine (MPc) formed a multi-layer over the surface of the electrode, which could be removed to leave a monolayer with a mass loading that compared favourably to the theoretical value expected. Analysis of frequency and dissipation plots indicated covalent attachment of glucose oxidase onto the metallophthalocyanine layer. The amount of GOx bound using the model system compared favourably to calculations derived from the maximal amperometric functioning of the electrochemical sensor (examined in previously-published literature, Mashazi, P.N., Ozoemena, K.I., Nyokong, T., 2006. Electrochim. Acta 52, 177–186), but not to theoretical values derived from dimensions of GOx as established by crystallography. The strength of the binding of the GOx film with the TCACoPc layer was tested by using 2% SDS as a denaturant/surfactant, and the GOx film was not found to be significantly affected by exposure to this. This paper thus showed that QCM-D can be used in order to model essential processes and interactions that dictate the functional parameters of a biosensor.
- Full Text:
- Date Issued: 2007
Comparative electrooxidation of sulphite by self-assembled monolayers (SAMs) of Co (II), Fe (II), Ni (II) and Mn (III) tetrakis benzylmercapto and dodecylmercapto metallophthalocyanines complexes on gold electrodes
- Agboola, Bolade, Nyokong, Tebello
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281223 , vital:55703 , xlink:href="https://doi.org/10.1016/j.talanta.2006.11.042"
- Description: This work reports on the use of Co(II), Fe(II), Mn(III) and Ni(II) tetrakis benzylmercapto and dodecylmercapto phthalocyanine complexes for gold electrode modification for electrooxidation of sulphite ions. The complexes were successfully used to modify gold electrodes by self-assembled monolayer (SAM) technique. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, underpotential deposition (UPD) of copper and solution redox chemistry of [Fe(H2O)63+]/[Fe(H2O)62+]. All the modified electrodes showed improved catalytic activities than the unmodified gold electrode towards sulphite ion electrooxidation with all the modified electrodes exhibiting high resistance to electrode surface passivation. Better catalytic performance were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak, while the NiPcs which did not show metal based redox reaction performed less. The catalytic current was found to be linear with sulphite ion concentration in the concentration range employed in this work (0.1–1 mM) and sensitivities ranging from 1.68 to 2.96 μA/mM were observed for all the modified electrodes. Mechanisms of the catalytic oxidation of sulphite ions are proposed.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281223 , vital:55703 , xlink:href="https://doi.org/10.1016/j.talanta.2006.11.042"
- Description: This work reports on the use of Co(II), Fe(II), Mn(III) and Ni(II) tetrakis benzylmercapto and dodecylmercapto phthalocyanine complexes for gold electrode modification for electrooxidation of sulphite ions. The complexes were successfully used to modify gold electrodes by self-assembled monolayer (SAM) technique. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, underpotential deposition (UPD) of copper and solution redox chemistry of [Fe(H2O)63+]/[Fe(H2O)62+]. All the modified electrodes showed improved catalytic activities than the unmodified gold electrode towards sulphite ion electrooxidation with all the modified electrodes exhibiting high resistance to electrode surface passivation. Better catalytic performance were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak, while the NiPcs which did not show metal based redox reaction performed less. The catalytic current was found to be linear with sulphite ion concentration in the concentration range employed in this work (0.1–1 mM) and sensitivities ranging from 1.68 to 2.96 μA/mM were observed for all the modified electrodes. Mechanisms of the catalytic oxidation of sulphite ions are proposed.
- Full Text:
- Date Issued: 2007