Iron perchlorophthalocyanine and tetrasulfophthalocyanine catalyzed oxidation of cyclohexane using hydrogen peroxide, chloroperoxybenzoic acid and tert-butylhydroperoxide as oxidants
- Grootboom, Natasha, Nyokong, Tebello
- Authors: Grootboom, Natasha , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289606 , vital:56653 , xlink:href="https://doi.org/10.1016/S1381-1169(01)00404-6"
- Description: Polychlorophthalocyanine (Cl16PcFeII) and tetrasulfophthalocyanine ([FeIITSPc]4−) complexes of iron are employed as catalysts for the oxidation of cyclohexane using tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (m-CPBA) and hydrogen peroxide as oxidants. Catalysis using the Cl16PcFeII was performed in a dimethylformamide:dichloromethane (3:7) solvent mixture. For the [FeIITSPc]4−catalyst, a water:methanol (1:9) mixture was employed. The products of the catalysis are cyclohexanone, cyclohexanol and cyclohexanediol. The relative yields of the products depended on oxidant and the catalyst. TBHP was found to be the best oxidant since minimal destruction of the catalyst and higher selectivity in the products were observed when this oxidant was employed. The mechanism of the oxidation of cyclohexane in the presence of the Cl16PcFeII and [FeIITSPc]4− involves the oxidation of these catalysts, forming an Fe(III) phthalocyanine species as an intermediate. Higher yields were observed when [FeTSPc]4− was employed as a catalyst, which is more soluble than the perchlorinated iron phthalocyanine catalyst.
- Full Text:
- Date Issued: 2002
- Authors: Grootboom, Natasha , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289606 , vital:56653 , xlink:href="https://doi.org/10.1016/S1381-1169(01)00404-6"
- Description: Polychlorophthalocyanine (Cl16PcFeII) and tetrasulfophthalocyanine ([FeIITSPc]4−) complexes of iron are employed as catalysts for the oxidation of cyclohexane using tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (m-CPBA) and hydrogen peroxide as oxidants. Catalysis using the Cl16PcFeII was performed in a dimethylformamide:dichloromethane (3:7) solvent mixture. For the [FeIITSPc]4−catalyst, a water:methanol (1:9) mixture was employed. The products of the catalysis are cyclohexanone, cyclohexanol and cyclohexanediol. The relative yields of the products depended on oxidant and the catalyst. TBHP was found to be the best oxidant since minimal destruction of the catalyst and higher selectivity in the products were observed when this oxidant was employed. The mechanism of the oxidation of cyclohexane in the presence of the Cl16PcFeII and [FeIITSPc]4− involves the oxidation of these catalysts, forming an Fe(III) phthalocyanine species as an intermediate. Higher yields were observed when [FeTSPc]4− was employed as a catalyst, which is more soluble than the perchlorinated iron phthalocyanine catalyst.
- Full Text:
- Date Issued: 2002
Synthesis, electrochemical and photochemical properties of unsymmetrically substituted zinc phthalocyanine complexes
- Matlaba, Pulane M, Nyokong, Tebello
- Authors: Matlaba, Pulane M , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289650 , vital:56658 , xlink:href="https://doi.org/10.1016/S0277-5387(02)01226-3"
- Description: The synthesis of symmetrically and unsymmetrically substituted zinc phthalocyanine (ZnPc) derivatives are reported. The ZnPc derivatives are synthesized by ring expansion of subphthalocyanine complexes. Ring substitution is effected with tert-butyl phenol, naphthol and hydroxybenzoic acid. Comparison of the redox potentials for complexes substituted with varying numbers of tert-butyl phenol: 1 (complex 5), 2 (complex 6), 3 (complex 7), 6 (complex 8) and 8 (complex 9) shows that the complexes with the highest number of substituents are more difficult to oxidize and easier to reduce. All the reported complexes are relatively photostable, with photobleaching quantum yields of the order of 10−5. Singlet oxygen quantum yields for the complexes ranged from 0.22 to 0.68.
- Full Text:
- Date Issued: 2002
- Authors: Matlaba, Pulane M , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289650 , vital:56658 , xlink:href="https://doi.org/10.1016/S0277-5387(02)01226-3"
- Description: The synthesis of symmetrically and unsymmetrically substituted zinc phthalocyanine (ZnPc) derivatives are reported. The ZnPc derivatives are synthesized by ring expansion of subphthalocyanine complexes. Ring substitution is effected with tert-butyl phenol, naphthol and hydroxybenzoic acid. Comparison of the redox potentials for complexes substituted with varying numbers of tert-butyl phenol: 1 (complex 5), 2 (complex 6), 3 (complex 7), 6 (complex 8) and 8 (complex 9) shows that the complexes with the highest number of substituents are more difficult to oxidize and easier to reduce. All the reported complexes are relatively photostable, with photobleaching quantum yields of the order of 10−5. Singlet oxygen quantum yields for the complexes ranged from 0.22 to 0.68.
- Full Text:
- Date Issued: 2002
Voltammetric characterization of the self-assembled monolayer (SAM) of octabutylthiophthalocyaninatoiron (II)
- Ozoemena,Kenneth, Nyokong, Tebello
- Authors: Ozoemena,Kenneth , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290419 , vital:56748 , xlink:href="https://doi.org/10.1016/S0013-4686(02)00362-6"
- Description: The fabrication of a self-assembled monolayer (SAM) of 2,3,9,10,16,17,23,24-octa (butylthio)-phthalocyaninatoiron(II) [FePc(SBu)8] on gold electrode is described. The integrity of the SAM, with respect to its ability to block certain Faradaic processes, is interrogated using cyclic voltammetric experiments in aqueous solutions. The experiments show that this SAM provide an excellent blocking capability to the Faradaic processes emanating from gold surface oxidation, underpotential deposition (UPD) of copper and redox chemistry of Fe(NH4)(SO4)2 in HClO4. It is revealed by cyclic voltammetry that an ill-defined reversible couple of the SAM of FePc(SBu)8 can be greatly improved by a simple repetitive cycling of the modified electrode in a DMF solution containing TBAP within a short space of time (ca. 2 min). This ‘activation’ process provides good information concerning the surface coverage and orientation of the monolayer. The reversible redox wave shows a potential shift of about −57 mV per pH in the pH range of 2–9. A preliminary investigation indicates that FePc(SBu)8-SAM modified gold electrode shows electrocatalytic activity toward the oxidation of L-cysteine in acidic medium. The monolayer is stable and easily reproducible. However, due to its susceptibility to destruction via oxidative and reductive desorptions, its potential application as an electrochemical sensor would be much better in acidic and neutral than alkaline environments.
- Full Text:
- Date Issued: 2002
- Authors: Ozoemena,Kenneth , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290419 , vital:56748 , xlink:href="https://doi.org/10.1016/S0013-4686(02)00362-6"
- Description: The fabrication of a self-assembled monolayer (SAM) of 2,3,9,10,16,17,23,24-octa (butylthio)-phthalocyaninatoiron(II) [FePc(SBu)8] on gold electrode is described. The integrity of the SAM, with respect to its ability to block certain Faradaic processes, is interrogated using cyclic voltammetric experiments in aqueous solutions. The experiments show that this SAM provide an excellent blocking capability to the Faradaic processes emanating from gold surface oxidation, underpotential deposition (UPD) of copper and redox chemistry of Fe(NH4)(SO4)2 in HClO4. It is revealed by cyclic voltammetry that an ill-defined reversible couple of the SAM of FePc(SBu)8 can be greatly improved by a simple repetitive cycling of the modified electrode in a DMF solution containing TBAP within a short space of time (ca. 2 min). This ‘activation’ process provides good information concerning the surface coverage and orientation of the monolayer. The reversible redox wave shows a potential shift of about −57 mV per pH in the pH range of 2–9. A preliminary investigation indicates that FePc(SBu)8-SAM modified gold electrode shows electrocatalytic activity toward the oxidation of L-cysteine in acidic medium. The monolayer is stable and easily reproducible. However, due to its susceptibility to destruction via oxidative and reductive desorptions, its potential application as an electrochemical sensor would be much better in acidic and neutral than alkaline environments.
- Full Text:
- Date Issued: 2002
Direct-use value of smallholder crop production in a semi-arid rural South African village
- Dovie, Delali B K, Witkowski, Ed T F, Shackleton, Charlie M
- Authors: Dovie, Delali B K , Witkowski, Ed T F , Shackleton, Charlie M
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181595 , vital:43750 , xlink:href="https://doi.org/10.1016/S0308-521X(02)00124-5"
- Description: The monetary value of natural resources used by rural communities for subsistence is important when addressing issues affecting the livelihoods of impoverished rural households. There is therefore the need to attribute monetary values to non-marketed products from smallholder production systems in order to reliably account for resource availability and usage to further sound policy decisions. The objective of this paper is to present an empirical analysis of the direct-use and traded values of crop production by households, and to discuss the implications for policy development. The study was undertaken in combination with an evaluation of other livelihood sectors in Thorndale, a semi-arid rural village in the Limpopo province of South Africa. The net direct-use value of crops was estimated at $443.4 per household per annum across the village. Maize (Zea mays), watermelon (Citrullus, vulgaris), peanuts (Arachis hypogaea) and common beans (Phaseolus vulgaris) contributed over 90% to the total direct-use value of crops. Maize alone contributed 40% of this value per household at an estimated $652/ha. Marketing of resources was not a common practice, limited to only maize and peanuts. Farming was basically a rain-fed–mixed cropping system with low production inputs. Farmer support services, human capital development and tenure security were major areas identified for policy development.
- Full Text:
- Date Issued: 2003
- Authors: Dovie, Delali B K , Witkowski, Ed T F , Shackleton, Charlie M
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181595 , vital:43750 , xlink:href="https://doi.org/10.1016/S0308-521X(02)00124-5"
- Description: The monetary value of natural resources used by rural communities for subsistence is important when addressing issues affecting the livelihoods of impoverished rural households. There is therefore the need to attribute monetary values to non-marketed products from smallholder production systems in order to reliably account for resource availability and usage to further sound policy decisions. The objective of this paper is to present an empirical analysis of the direct-use and traded values of crop production by households, and to discuss the implications for policy development. The study was undertaken in combination with an evaluation of other livelihood sectors in Thorndale, a semi-arid rural village in the Limpopo province of South Africa. The net direct-use value of crops was estimated at $443.4 per household per annum across the village. Maize (Zea mays), watermelon (Citrullus, vulgaris), peanuts (Arachis hypogaea) and common beans (Phaseolus vulgaris) contributed over 90% to the total direct-use value of crops. Maize alone contributed 40% of this value per household at an estimated $652/ha. Marketing of resources was not a common practice, limited to only maize and peanuts. Farming was basically a rain-fed–mixed cropping system with low production inputs. Farmer support services, human capital development and tenure security were major areas identified for policy development.
- Full Text:
- Date Issued: 2003
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
Electrochemical behaviour of thiol-derivatised zinc (II) phthalocyanine complexes and their self-immobilised films at gold electrodes
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290295 , vital:56737 , xlink:href="https://doi.org/10.1016/j.microc.2003.08.002"
- Description: Electrochemical properties of novel, peripherally substituted zinc phthalocyanine complex, octa(4-methylphenylthio-) phthalocyaninatozinc(II) [ZnPc(SC6H4CH3)8] (1a) in DMF solution are presented. This complex showed five quasi-reversible/reversible, diffusion-controlled redox couples. Solution voltammetry of 1a showed little contrast with that of its alkythiol-derivative, octabutylthiophthalocyaninatozinc(II) [ZnPc(SC4H9)8] (1b) in that both thiol-substituents tend to show electron-withdrawing influence on the phthalocyanine ligands; complex 1a showing easier reduction and more difficult to oxidation when compared to 1b and other alkyl derivatives. The voltammetric features of the solid ultrathin films of 1a and 1b, immobilized on gold electrodes via the self-assembling technique, are also presented. Interestingly, the self-assembled films are stable and reproducible and provide good suppression to the following Faradaic processes; gold surface oxidation, solution ion species and underpotential deposition (UPD) of copper.
- Full Text:
- Date Issued: 2003
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290295 , vital:56737 , xlink:href="https://doi.org/10.1016/j.microc.2003.08.002"
- Description: Electrochemical properties of novel, peripherally substituted zinc phthalocyanine complex, octa(4-methylphenylthio-) phthalocyaninatozinc(II) [ZnPc(SC6H4CH3)8] (1a) in DMF solution are presented. This complex showed five quasi-reversible/reversible, diffusion-controlled redox couples. Solution voltammetry of 1a showed little contrast with that of its alkythiol-derivative, octabutylthiophthalocyaninatozinc(II) [ZnPc(SC4H9)8] (1b) in that both thiol-substituents tend to show electron-withdrawing influence on the phthalocyanine ligands; complex 1a showing easier reduction and more difficult to oxidation when compared to 1b and other alkyl derivatives. The voltammetric features of the solid ultrathin films of 1a and 1b, immobilized on gold electrodes via the self-assembling technique, are also presented. Interestingly, the self-assembled films are stable and reproducible and provide good suppression to the following Faradaic processes; gold surface oxidation, solution ion species and underpotential deposition (UPD) of copper.
- Full Text:
- Date Issued: 2003
Phthalocyanines and related complexes as electrocatalysts for the detection of nitric oxide
- Nyokong, Tebello, Vilakazi, Sibulelo
- Authors: Nyokong, Tebello , Vilakazi, Sibulelo
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290346 , vital:56741 , xlink:href="https://doi.org/10.1016/S0039-9140(03)00356-4"
- Description: Metallophthalocyanine (MPc) and metalloporphyrin complexes as well as some metalloproteins including myoglobin, hemoglobin, cyanocobalamin and cytochrome c catalyse the detection of nitric oxide (NO). The catalytic process often involve changes in the oxidation state of the catalyst. These complexes catalyse both the reduction and oxidation of NO. MPc complexes containing electroactive central metals such as CoPc and FePc generally show better catalytic activity towards the detection of NO than complexes containing electroinacive central metals. However, the involvement of ring based redox processes was confirmed for the homogenous NO catalysis using CoPc.
- Full Text:
- Date Issued: 2003
- Authors: Nyokong, Tebello , Vilakazi, Sibulelo
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290346 , vital:56741 , xlink:href="https://doi.org/10.1016/S0039-9140(03)00356-4"
- Description: Metallophthalocyanine (MPc) and metalloporphyrin complexes as well as some metalloproteins including myoglobin, hemoglobin, cyanocobalamin and cytochrome c catalyse the detection of nitric oxide (NO). The catalytic process often involve changes in the oxidation state of the catalyst. These complexes catalyse both the reduction and oxidation of NO. MPc complexes containing electroactive central metals such as CoPc and FePc generally show better catalytic activity towards the detection of NO than complexes containing electroinacive central metals. However, the involvement of ring based redox processes was confirmed for the homogenous NO catalysis using CoPc.
- Full Text:
- Date Issued: 2003
Synthesis, spectroscopy and photochemistry of octasubstituted thiol-derivatized phthalocyaninatozinc (II) complexes
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290401 , vital:56746 , xlink:href="https://doi.org/10.1016/S1387-7003(03)00218-1"
- Description: Synthesis, spectroscopic and photochemical characterization of phenylthiol-derivatized zinc phthalocyanine complex: 2,3,9,10,16,17,23,24-octa(4-methylphenylthio-)phthalocyaninatozinc(II) [ZnPc(SC6H4CH3)8] (3a) and its alkanethiol derivative, 2,3,9,10,16,17,23,24-octabutylthiophthalocyaninatozinc(II) [ZnPc(SC4H9)8] (3b) are described. Spectroscopic analyses show that 3a has a higher aggregation tendency than 3b in organic solvents. Photochemical studies indicate that 3b is more photostable and more efficient at singlet oxygen generation than 3a.
- Full Text:
- Date Issued: 2003
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290401 , vital:56746 , xlink:href="https://doi.org/10.1016/S1387-7003(03)00218-1"
- Description: Synthesis, spectroscopic and photochemical characterization of phenylthiol-derivatized zinc phthalocyanine complex: 2,3,9,10,16,17,23,24-octa(4-methylphenylthio-)phthalocyaninatozinc(II) [ZnPc(SC6H4CH3)8] (3a) and its alkanethiol derivative, 2,3,9,10,16,17,23,24-octabutylthiophthalocyaninatozinc(II) [ZnPc(SC4H9)8] (3b) are described. Spectroscopic analyses show that 3a has a higher aggregation tendency than 3b in organic solvents. Photochemical studies indicate that 3b is more photostable and more efficient at singlet oxygen generation than 3a.
- Full Text:
- Date Issued: 2003
Catalytic activity of iron and cobalt phthalocyanine complexes towards the oxidation of cyclohexene using tert-butylhydroperoxide and chloroperoxybenzoic acid
- Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290257 , vital:56729 , xlink:href="https://doi.org/10.1016/j.molcata.2003.08.014"
- Description: Cyclohexene oxidation using tert-butylhydroperoxide (TBHP) or chloroperoxybenzoic acid (CPBA) in the presence of iron(II) polychlorophthalocyanine (Cl16PcFe), iron(II) phthalocyanine (PcFe) and cobalt(II) phthalocyanine (PcCo), results in the formation of the following products: cyclohexene oxide, 2-cyclohexene-1-ol and 2-cyclohexene-1-one. Adipic acid was also formed after long reaction times. The selectivity for 2-cyclohexene-1-one is favoured when Cl16PcFe or PcCo catalysts are employed, while PcFe is selective towards the formation of 2-cyclohexene-1-ol. The Cl16PcFe catalyst is transformed into a μ-oxo dimer (Cl16PcFeIIIOIIIFePcCl16) during the oxidation process. The catalytic process using the unsubstituted PcCoII and PcFeII catalysts involved PcMIII species as an intermediate. The active form of the Cl16PcFe catalyst was stable to degradation in that it was still active even after 4 weeks of continued catalysis.
- Full Text:
- Date Issued: 2004
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290257 , vital:56729 , xlink:href="https://doi.org/10.1016/j.molcata.2003.08.014"
- Description: Cyclohexene oxidation using tert-butylhydroperoxide (TBHP) or chloroperoxybenzoic acid (CPBA) in the presence of iron(II) polychlorophthalocyanine (Cl16PcFe), iron(II) phthalocyanine (PcFe) and cobalt(II) phthalocyanine (PcCo), results in the formation of the following products: cyclohexene oxide, 2-cyclohexene-1-ol and 2-cyclohexene-1-one. Adipic acid was also formed after long reaction times. The selectivity for 2-cyclohexene-1-one is favoured when Cl16PcFe or PcCo catalysts are employed, while PcFe is selective towards the formation of 2-cyclohexene-1-ol. The Cl16PcFe catalyst is transformed into a μ-oxo dimer (Cl16PcFeIIIOIIIFePcCl16) during the oxidation process. The catalytic process using the unsubstituted PcCoII and PcFeII catalysts involved PcMIII species as an intermediate. The active form of the Cl16PcFe catalyst was stable to degradation in that it was still active even after 4 weeks of continued catalysis.
- Full Text:
- Date Issued: 2004
Electrochemical and catalytic properties of chromium tetraaminophthalocyanine
- Obirai, Joe, Nyokong, Tebello
- Authors: Obirai, Joe , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300310 , vital:57915 , xlink:href="https://doi.org/10.1016/j.jelechem.2004.06.026"
- Description: Chromium tetraaminophthalocyanine (CrIIITAPc) has been synthesized and its electrochemical and spectroelectrochemical properties reported. The first reduction and oxidation in this complex occur at the central metal, giving CrIITAPc and CrIVTAPc complexes, respectively, the latter having been observed for the first time. The CrIIITAPc species was polymerized onto glassy carbon (GCE) or indium tin oxide (ITO) electrodes and the polymer evolution confirmed by UV/Visible spectroscopy and by scanning electron microscopy. The polymers were employed for the catalytic oxidation of nitrite or nitric oxide, and the catalysis involved the CrIVTAPc−1 species.
- Full Text:
- Date Issued: 2004
- Authors: Obirai, Joe , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300310 , vital:57915 , xlink:href="https://doi.org/10.1016/j.jelechem.2004.06.026"
- Description: Chromium tetraaminophthalocyanine (CrIIITAPc) has been synthesized and its electrochemical and spectroelectrochemical properties reported. The first reduction and oxidation in this complex occur at the central metal, giving CrIITAPc and CrIVTAPc complexes, respectively, the latter having been observed for the first time. The CrIIITAPc species was polymerized onto glassy carbon (GCE) or indium tin oxide (ITO) electrodes and the polymer evolution confirmed by UV/Visible spectroscopy and by scanning electron microscopy. The polymers were employed for the catalytic oxidation of nitrite or nitric oxide, and the catalysis involved the CrIVTAPc−1 species.
- Full Text:
- Date Issued: 2004
Electrochemical studies of manganese tetraamminophthalocyanine monomer and polymer
- Obirai, Joseph, Nyokong, Tebello
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290330 , vital:56738 , xlink:href="https://doi.org/10.1016/j.electacta.2003.11.006"
- Description: Manganese tetraaminophthalocyanine (MnTAPc) has been synthesised. The cyclic voltammetry and spectroelectrochemistry of the complex have been examined. Spectroelectrochemistry has been used to confirm that the species synthesised in this work contains MnIII, giving (OH)MnIIITAPc. The oxidation and reduction couples obtained from cyclic voltammetry have been assigned to MnIVPc−/MnIVPc2− (couple I), MnIVPc2−/MnIIIPc2− (couple I′), MnIIIPc2−/MnIIPc2− (couple II) and MnIIPc2−/MnIIPc3− (couple III). Electropolymerization of the MnTAPc onto either the indium tin oxide or glassy carbon electrode results in the in the formation of a poly-MnTAPc. The poly-MnTAPc shows improved reversibility at low pH. The poly-MnTAPc electrode was employed to analyse glycine.
- Full Text:
- Date Issued: 2004
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290330 , vital:56738 , xlink:href="https://doi.org/10.1016/j.electacta.2003.11.006"
- Description: Manganese tetraaminophthalocyanine (MnTAPc) has been synthesised. The cyclic voltammetry and spectroelectrochemistry of the complex have been examined. Spectroelectrochemistry has been used to confirm that the species synthesised in this work contains MnIII, giving (OH)MnIIITAPc. The oxidation and reduction couples obtained from cyclic voltammetry have been assigned to MnIVPc−/MnIVPc2− (couple I), MnIVPc2−/MnIIIPc2− (couple I′), MnIIIPc2−/MnIIPc2− (couple II) and MnIIPc2−/MnIIPc3− (couple III). Electropolymerization of the MnTAPc onto either the indium tin oxide or glassy carbon electrode results in the in the formation of a poly-MnTAPc. The poly-MnTAPc shows improved reversibility at low pH. The poly-MnTAPc electrode was employed to analyse glycine.
- Full Text:
- Date Issued: 2004
Zinc phthalocyanine photocatalyzed oxidation of cyclohexene
- Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289399 , vital:56629 , xlink:href="https://doi.org/10.1016/j.molcata.2004.05.010"
- Description: Cyclohexene photooxidation catalyzed by zinc phthalocyanine (ZnPc) using either red or white light results in the formation of cyclohexenone, cyclohexenol, trans-cyclohexanediol, cyclohexene oxide and cyclohexene hydroperoxide. The product yield increased as follows: cyclohexenone > cyclohexenol > trans-cyclohexanediol > cyclohexene oxide > cyclohexene hydroperoxide. The mechanism for the formation of these products involves both singlet oxygen and radicals (Type II and Type I mechanisms, respectively). The catalyst degraded slowly when low light intensities were employed. The product yields were found to depend on the light intensity, the nature of solvent, irradiation time and the rate of photodegradation of the catalyst.
- Full Text:
- Date Issued: 2004
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289399 , vital:56629 , xlink:href="https://doi.org/10.1016/j.molcata.2004.05.010"
- Description: Cyclohexene photooxidation catalyzed by zinc phthalocyanine (ZnPc) using either red or white light results in the formation of cyclohexenone, cyclohexenol, trans-cyclohexanediol, cyclohexene oxide and cyclohexene hydroperoxide. The product yield increased as follows: cyclohexenone > cyclohexenol > trans-cyclohexanediol > cyclohexene oxide > cyclohexene hydroperoxide. The mechanism for the formation of these products involves both singlet oxygen and radicals (Type II and Type I mechanisms, respectively). The catalyst degraded slowly when low light intensities were employed. The product yields were found to depend on the light intensity, the nature of solvent, irradiation time and the rate of photodegradation of the catalyst.
- Full Text:
- Date Issued: 2004
Electro-oxidation of phenol and its derivatives on poly-Ni (OH) TPhPyPc modified vitreous carbon electrodes
- Obirai, Joseph, Bedioui, Fethi, Nyokong, Tebello
- Authors: Obirai, Joseph , Bedioui, Fethi , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289353 , vital:56625 , xlink:href="https://doi.org/10.1016/j.jelechem.2004.11.006"
- Description: The electrochemical oxidation of phenol and its derivatives using poly-nickel hydroxy tetraphenoxypyrrolephthalocyanine (poly-Ni(OH)TPhPyPc) modified vitreous carbon electrodes are described. The films were formed by the electro-transformation of the electropolymerized pyrrole-substituted phenoxyphthalocyanine poly-NiTPhPyPc modified electrode in aqueous 0.1 M NaOH solution. The poly-Ni(OH)TPhPyPc films showed better stability and resistance to electrode fouling compared to poly-NiTPhPyPc and unmodified electrodes. The resistance to surface fouling and stability can be attributed to the structure of the ring substituent on the phthalocyanine macrocycle and to the particular O–Ni–O bridged architecture of the nickel phthalocyanine film.
- Full Text:
- Date Issued: 2005
- Authors: Obirai, Joseph , Bedioui, Fethi , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289353 , vital:56625 , xlink:href="https://doi.org/10.1016/j.jelechem.2004.11.006"
- Description: The electrochemical oxidation of phenol and its derivatives using poly-nickel hydroxy tetraphenoxypyrrolephthalocyanine (poly-Ni(OH)TPhPyPc) modified vitreous carbon electrodes are described. The films were formed by the electro-transformation of the electropolymerized pyrrole-substituted phenoxyphthalocyanine poly-NiTPhPyPc modified electrode in aqueous 0.1 M NaOH solution. The poly-Ni(OH)TPhPyPc films showed better stability and resistance to electrode fouling compared to poly-NiTPhPyPc and unmodified electrodes. The resistance to surface fouling and stability can be attributed to the structure of the ring substituent on the phthalocyanine macrocycle and to the particular O–Ni–O bridged architecture of the nickel phthalocyanine film.
- Full Text:
- Date Issued: 2005
Electrocatalytic oxidation and detection of hydrazine at gold electrode modified with iron phthalocyanine complex linked to mercaptopyridine self-assembled monolayer
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286065 , vital:56235 , xlink:href="https://doi.org/10.1016/j.talanta.2005.02.030"
- Description: Electrocatalytic oxidation and detection of hydrazine in pH 7.0 conditions were studied by using gold electrode modified with self-assembled monolayer (SAM) films of iron phthalocyanine (FePc) complex axially ligated to a preformed 4-mercaptopyridine SAMs. The anodic oxidation of hydrazine in neutral pH conditions with FePc-linked-mercaptopyridine-SAM-modified gold electrode occurred at low overpotential (0.35 V versus Ag|AgCl) and the treatment of the voltammetric data showed that it was a pure diffusion-controlled reaction with the involvement of one electron in the rate-determining step. The mechanism for the interaction of hydrazine with the FePc-SAM is proposed to involve the Fe(III)Pc/Fe(II)Pc redox process. Using cyclic voltammetry (CV) and Osteryoung square wave voltammetry (OSWV), hydrazine was detected over a linear concentration range of 1.3 × 10−5 to 9.2 × 10−5 mol/L with low limits of detection (ca. 5 and 11 μM for OSWV and CV, respectively). At concentrations higher than 1.2 × 10−4 mol/L the anodic peak potential shifted to 0.40 V (versus Ag|AgCl), and this was interpreted to be due to kinetic limitations resulting from the saturation of hydrazine and its oxidation products onto the redox-active monolayer film. This type of metallophthalocyanine-SAM-based electrode is a highly promising electrochemical sensor given its ease of fabrication, good catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286065 , vital:56235 , xlink:href="https://doi.org/10.1016/j.talanta.2005.02.030"
- Description: Electrocatalytic oxidation and detection of hydrazine in pH 7.0 conditions were studied by using gold electrode modified with self-assembled monolayer (SAM) films of iron phthalocyanine (FePc) complex axially ligated to a preformed 4-mercaptopyridine SAMs. The anodic oxidation of hydrazine in neutral pH conditions with FePc-linked-mercaptopyridine-SAM-modified gold electrode occurred at low overpotential (0.35 V versus Ag|AgCl) and the treatment of the voltammetric data showed that it was a pure diffusion-controlled reaction with the involvement of one electron in the rate-determining step. The mechanism for the interaction of hydrazine with the FePc-SAM is proposed to involve the Fe(III)Pc/Fe(II)Pc redox process. Using cyclic voltammetry (CV) and Osteryoung square wave voltammetry (OSWV), hydrazine was detected over a linear concentration range of 1.3 × 10−5 to 9.2 × 10−5 mol/L with low limits of detection (ca. 5 and 11 μM for OSWV and CV, respectively). At concentrations higher than 1.2 × 10−4 mol/L the anodic peak potential shifted to 0.40 V (versus Ag|AgCl), and this was interpreted to be due to kinetic limitations resulting from the saturation of hydrazine and its oxidation products onto the redox-active monolayer film. This type of metallophthalocyanine-SAM-based electrode is a highly promising electrochemical sensor given its ease of fabrication, good catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
Hydrogen peroxide oxidation of 2-chlorophenol and 2, 4, 5-trichlorophenol catalyzed by monomeric and aggregated cobalt tetrasulfophthalocyanine
- Agboola, Bolade, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289249 , vital:56612 , xlink:href="https://doi.org/10.1016/j.molcata.2004.10.041"
- Description: Cobalt tetrasulfophthalocyanine (CoTSPc) was used to catalyze the oxidation of 2-chlorophenol (2-CP) and 2,4,5-trichlorophenol (TCP) using hydrogen peroxide (H2O2) as the oxidant. This CoTSPc catalyzed hydrogen peroxide oxidation of chlorophenols resulted in the formation of different types of oxidation products depending on the solvent conditions. In water/methanol conditions (where CoTSPc is mainly monomeric, and unionized forms of the phenols), phenol and hydroquinone were the main oxidation products, while in phosphate buffer solutions (pH 7 and 10 for TCP and 2-CP, respectively, where CoTSPc is mainly aggregated, and ionized forms of the phenols), benzoquinone was the main product. In contrast to CoTSPc, other MTSPc complexes studied (AlTSPc, CuTSPc and NiTSPc) exhibited no detectable catalytic effect on the oxidation of chlorophenols under the experimental conditions employed, thus proving the effect of the central metal ions on efficient catalysis of chlorophenol. Reaction pathways are proposed based on the relative time of oxidation products formation.
- Full Text:
- Date Issued: 2005
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289249 , vital:56612 , xlink:href="https://doi.org/10.1016/j.molcata.2004.10.041"
- Description: Cobalt tetrasulfophthalocyanine (CoTSPc) was used to catalyze the oxidation of 2-chlorophenol (2-CP) and 2,4,5-trichlorophenol (TCP) using hydrogen peroxide (H2O2) as the oxidant. This CoTSPc catalyzed hydrogen peroxide oxidation of chlorophenols resulted in the formation of different types of oxidation products depending on the solvent conditions. In water/methanol conditions (where CoTSPc is mainly monomeric, and unionized forms of the phenols), phenol and hydroquinone were the main oxidation products, while in phosphate buffer solutions (pH 7 and 10 for TCP and 2-CP, respectively, where CoTSPc is mainly aggregated, and ionized forms of the phenols), benzoquinone was the main product. In contrast to CoTSPc, other MTSPc complexes studied (AlTSPc, CuTSPc and NiTSPc) exhibited no detectable catalytic effect on the oxidation of chlorophenols under the experimental conditions employed, thus proving the effect of the central metal ions on efficient catalysis of chlorophenol. Reaction pathways are proposed based on the relative time of oxidation products formation.
- Full Text:
- Date Issued: 2005
Immobilized cobalt (II) phthalocyanine–cobalt (II) porphyrin pentamer at a glassy carbon electrode
- Ozoemena, Kenneth I, Zhao, Zhixin, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Zhao, Zhixin , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300322 , vital:57916 , xlink:href="https://doi.org/10.1016/j.elecom.2005.04.019"
- Description: This communication describes the electrochemistry of a novel cobalt phthalocyanine–cobalt porphyrin (cobalt(II)phthalocyanine–cobalt(II)tetra(5-phenoxy-10,15,20-triphenylporphyrin)) (CoPc-(CoTPP)4) immobilised onto a glassy carbon electrode (GCE). The GCE-CoPc-(CoTPP)4 displayed high efficiency as a potential amperometric sensor for hydrogen peroxide (H2O2) in neutral and alkaline pH conditions. Electrochemical and electrocatalytic properties of the pentamer seem to depend mostly on the central CoPc, and partly, on the synergistic effect of the CoPc/CoPP units. The GCE-CoPc-(CoTPP)4 showed very fast amperometric response (∼1 s), with linearities up to ⩾1.50 mM, low detection limits (μM range) and stability (8 weeks) towards the amperometric determination of laboratory and medical solutions of H2O2.
- Full Text:
- Date Issued: 2005
- Authors: Ozoemena, Kenneth I , Zhao, Zhixin , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300322 , vital:57916 , xlink:href="https://doi.org/10.1016/j.elecom.2005.04.019"
- Description: This communication describes the electrochemistry of a novel cobalt phthalocyanine–cobalt porphyrin (cobalt(II)phthalocyanine–cobalt(II)tetra(5-phenoxy-10,15,20-triphenylporphyrin)) (CoPc-(CoTPP)4) immobilised onto a glassy carbon electrode (GCE). The GCE-CoPc-(CoTPP)4 displayed high efficiency as a potential amperometric sensor for hydrogen peroxide (H2O2) in neutral and alkaline pH conditions. Electrochemical and electrocatalytic properties of the pentamer seem to depend mostly on the central CoPc, and partly, on the synergistic effect of the CoPc/CoPP units. The GCE-CoPc-(CoTPP)4 showed very fast amperometric response (∼1 s), with linearities up to ⩾1.50 mM, low detection limits (μM range) and stability (8 weeks) towards the amperometric determination of laboratory and medical solutions of H2O2.
- Full Text:
- Date Issued: 2005
Modelling the sustainable harvest of Sclerocarya birrea subsp. caffra fruits in the South African lowveld
- Emanuel, P L, Shackleton, Charlie M, Baxter, Jeremy
- Authors: Emanuel, P L , Shackleton, Charlie M , Baxter, Jeremy
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181312 , vital:43718 , xlink:href="https://doi.org/10.1016/j.foreco.2005.03.066"
- Description: Levels of commercialization, size class profile and fruit production of Sclerocarya birrea (marula) trees were studied in the Bushbuckridge region of South Africa. A stage-based population matrix model was used to estimate the sustainable yield for S. birrea fruit. The trees begin to bear fruit at an average size of 42.8 cm in circumference and this relates to an approximate age of 19 years. For a stable size class profile, the population growth rate, λ, was 1.1828758. The observed size class profile did not conform to the stable stage size class profile, obtained from the model. Thus, it was not possible to predict the state of the observed population. Using the model, it was estimated that 92% of fruit could be removed without impacting the current population profile. The management of other more destructive forms of S. birrea resource use (such as bark or firewood harvesting), however, do need to be monitored to limit negative impacts on the population that may reduce fruit availability for regeneration or cropping.
- Full Text:
- Date Issued: 2005
- Authors: Emanuel, P L , Shackleton, Charlie M , Baxter, Jeremy
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181312 , vital:43718 , xlink:href="https://doi.org/10.1016/j.foreco.2005.03.066"
- Description: Levels of commercialization, size class profile and fruit production of Sclerocarya birrea (marula) trees were studied in the Bushbuckridge region of South Africa. A stage-based population matrix model was used to estimate the sustainable yield for S. birrea fruit. The trees begin to bear fruit at an average size of 42.8 cm in circumference and this relates to an approximate age of 19 years. For a stable size class profile, the population growth rate, λ, was 1.1828758. The observed size class profile did not conform to the stable stage size class profile, obtained from the model. Thus, it was not possible to predict the state of the observed population. Using the model, it was estimated that 92% of fruit could be removed without impacting the current population profile. The management of other more destructive forms of S. birrea resource use (such as bark or firewood harvesting), however, do need to be monitored to limit negative impacts on the population that may reduce fruit availability for regeneration or cropping.
- Full Text:
- Date Issued: 2005
Photophysical and photochemical studies of sulphonated non-transition metal phthalocyanines in aqueous and non-aqueous media
- Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289271 , vital:56614 , xlink:href="https://doi.org/10.1016/j.jphotochem.2005.03.001"
- Description: The photophysical and photochemical parameters for mixed sulphonated metallophthalocyanine complexes (AlPcSmix, SiPcSmix, GePcSmix, SnPcSmix, and ZnPcSmix) are reported in phosphate buffer saline (PBS, pH 7.4), PBS containing the surfactant Triton X-100, and in dimethylsulphoxide (DMSO). The ground state spectra of SiPcSmix, GePcSmix and SnPcSmix show splitting of the Q-band in DMSO, but the fluorescence spectra have only one band, suggesting that only some components of the mixed complexes fluoresce. In general the quantum yields of fluorescence (ΦF) were smaller in DMSO compared to the aqueous solvents, while quantum yields of triplet state (ΦT) were larger in DMSO. Triplet lifetimes were much lower in aqueous solutions (compared to DMSO) due to the fact that water absorbs strongly around 1108 nm, which corresponds to the triplet energy of a metallophthalocyanine complex. The MPcSmix complexes quenched hydroquinone, and the Stern–Volmer constants follow the order: AlPcSmix > SiPcSmix > GePcSmix > ZnPcSmix > SnPcSmix which is the order of the extinction coefficients (of the low energy band for complexes with split Q-band) of these molecules. The rate constants for fluorescence, intersystem crossing, internal conversion, and photodegradation were determined from the hydroquinone quenching data.
- Full Text:
- Date Issued: 2005
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289271 , vital:56614 , xlink:href="https://doi.org/10.1016/j.jphotochem.2005.03.001"
- Description: The photophysical and photochemical parameters for mixed sulphonated metallophthalocyanine complexes (AlPcSmix, SiPcSmix, GePcSmix, SnPcSmix, and ZnPcSmix) are reported in phosphate buffer saline (PBS, pH 7.4), PBS containing the surfactant Triton X-100, and in dimethylsulphoxide (DMSO). The ground state spectra of SiPcSmix, GePcSmix and SnPcSmix show splitting of the Q-band in DMSO, but the fluorescence spectra have only one band, suggesting that only some components of the mixed complexes fluoresce. In general the quantum yields of fluorescence (ΦF) were smaller in DMSO compared to the aqueous solvents, while quantum yields of triplet state (ΦT) were larger in DMSO. Triplet lifetimes were much lower in aqueous solutions (compared to DMSO) due to the fact that water absorbs strongly around 1108 nm, which corresponds to the triplet energy of a metallophthalocyanine complex. The MPcSmix complexes quenched hydroquinone, and the Stern–Volmer constants follow the order: AlPcSmix > SiPcSmix > GePcSmix > ZnPcSmix > SnPcSmix which is the order of the extinction coefficients (of the low energy band for complexes with split Q-band) of these molecules. The rate constants for fluorescence, intersystem crossing, internal conversion, and photodegradation were determined from the hydroquinone quenching data.
- Full Text:
- Date Issued: 2005
Surface electrochemistry of iron phthalocyanine axially ligated to 4-mercaptopyridine self-assembled monolayers at gold electrode
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289282 , vital:56615 , xlink:href="https://doi.org/10.1016/j.jelechem.2005.02.018"
- Description: Surface electrochemical behaviour of a self-immobilised iron phthalocyanine (FePc) ultrathin film, via axial ligation reaction, onto a preformed 4-mercaptopyridine self-assembled monolayer on gold electrode has been described. Electrochemical evidence for the sensor clearly suggested surface-confined, flat “umbrella”-oriented and densely-packed monolayer film structure. The proposed electrochemical sensor exhibited good catalytic activity towards the oxidation of thiocyanate in pH 4.0 medium over a linear range of three decades of concentration (ca. 10−6–10−3 mol dm−3) with a detection limit in the order of ∼10−7 mol dm−3. The sensor exhibited useful potential for the analysis of thiocyanate in human urine and saliva samples. The advantageous properties of this type of electrode as a sensor for thiocyanate lie in its ease of fabrication, excellent catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289282 , vital:56615 , xlink:href="https://doi.org/10.1016/j.jelechem.2005.02.018"
- Description: Surface electrochemical behaviour of a self-immobilised iron phthalocyanine (FePc) ultrathin film, via axial ligation reaction, onto a preformed 4-mercaptopyridine self-assembled monolayer on gold electrode has been described. Electrochemical evidence for the sensor clearly suggested surface-confined, flat “umbrella”-oriented and densely-packed monolayer film structure. The proposed electrochemical sensor exhibited good catalytic activity towards the oxidation of thiocyanate in pH 4.0 medium over a linear range of three decades of concentration (ca. 10−6–10−3 mol dm−3) with a detection limit in the order of ∼10−7 mol dm−3. The sensor exhibited useful potential for the analysis of thiocyanate in human urine and saliva samples. The advantageous properties of this type of electrode as a sensor for thiocyanate lie in its ease of fabrication, excellent catalytic activity, stability, sensitivity and simplicity.
- Full Text:
- Date Issued: 2005
Synthesis, electrochemical and electrocatalytic behaviour of thiophene-appended cobalt, manganese and zinc phthalocyanine complexes
- Obirai, Joseph, Nyokong, Tebello
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286103 , vital:56238 , xlink:href="https://doi.org/10.1016/j.electacta.2005.03.024"
- Description: This work reports on the syntheses of new thiophene tetra substituted cobalt, manganese and zinc phthalocyanine (CoTETPc, (Cl)MnTETPc and ZnTETPc) complexes. The redox processes due to the thiophene substituent on the ring of the metallophthalocyanines (MPcs) were observed, in addition to Pc ring and metal (for Co and Mn complexes) based redox activity. The electrocatalytic activity of the CoTETPc complex adsorbed on glassy carbon electrode (GCE) by drop/dry-thermal annealing was investigated using L-cysteine. The modified electrode was stable to repetitive use without any signs of deactivation by oxidation products and was used to determine L-cysteine at concentrations between 0.0015 and 1 mM in pH 4 aqueous conditions.
- Full Text:
- Date Issued: 2005
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286103 , vital:56238 , xlink:href="https://doi.org/10.1016/j.electacta.2005.03.024"
- Description: This work reports on the syntheses of new thiophene tetra substituted cobalt, manganese and zinc phthalocyanine (CoTETPc, (Cl)MnTETPc and ZnTETPc) complexes. The redox processes due to the thiophene substituent on the ring of the metallophthalocyanines (MPcs) were observed, in addition to Pc ring and metal (for Co and Mn complexes) based redox activity. The electrocatalytic activity of the CoTETPc complex adsorbed on glassy carbon electrode (GCE) by drop/dry-thermal annealing was investigated using L-cysteine. The modified electrode was stable to repetitive use without any signs of deactivation by oxidation products and was used to determine L-cysteine at concentrations between 0.0015 and 1 mM in pH 4 aqueous conditions.
- Full Text:
- Date Issued: 2005