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
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
Determination of 2′, 3′-Dideoxyinosine Using Iron (II) Phthalocyanine Modified Carbon Paste Electrode
- Ozoemena, Kenneth I, Stefan, Raluca-Ioana, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Stefan, Raluca-Ioana , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300298 , vital:57914 , xlink:href="https://doi.org/10.1081/AL-200031940"
- Description: An amperometric sensor, based on carbon paste impregnated with iron (II) phthalocyanine complex (FePc), has been constructed for the assay of anti‐HIV agent dideoxyinosine (didanosine, DDI). Using chronoamperometry (E = +1.04 V versus Ag/AgCl) technique, the amperometric sensor can be used reliably for dideoxyinosine assay at pH 7.4 phosphate buffer in the 1.5–9.5 nmol/L concentration range with a detection limit of 5.7 × 10−10 mol/L. The surface of the electrode can easily be regenerated by simple polishing, obtaining a fresh surface ready for use in a new assay. The new amperometric sensor proved to be highly reliable for the assay of dideoxyinosine purity in raw material as well as for the uniformity content test of Videx® tablets.
- Full Text:
- Date Issued: 2004
- Authors: Ozoemena, Kenneth I , Stefan, Raluca-Ioana , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300298 , vital:57914 , xlink:href="https://doi.org/10.1081/AL-200031940"
- Description: An amperometric sensor, based on carbon paste impregnated with iron (II) phthalocyanine complex (FePc), has been constructed for the assay of anti‐HIV agent dideoxyinosine (didanosine, DDI). Using chronoamperometry (E = +1.04 V versus Ag/AgCl) technique, the amperometric sensor can be used reliably for dideoxyinosine assay at pH 7.4 phosphate buffer in the 1.5–9.5 nmol/L concentration range with a detection limit of 5.7 × 10−10 mol/L. The surface of the electrode can easily be regenerated by simple polishing, obtaining a fresh surface ready for use in a new assay. The new amperometric sensor proved to be highly reliable for the assay of dideoxyinosine purity in raw material as well as for the uniformity content test of Videx® tablets.
- Full Text:
- Date Issued: 2004
Comparative efficiency of immobilized non-transition metal phthalocyanine photosensitizers for the visible light transformation of chlorophenols
- Agboola, Bolade, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286043 , vital:56233 , xlink:href="https://doi.org/10.1016/j.molcata.2005.12.009"
- Description: Photolysis of aqueous solutions of chlorophenols (4-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and pentachlorophenol) in the presence of immobilized non-transition metal phthalocyanine photosensitizers onto Amberlite® is presented. The photosensitizers studied are: Al (AlOCPc) and Zn (ZnOCPc) octacarboxyphthalocyanines; Al (AlPcS4) and Zn (ZnPcS4) tetrasulfophthalocyanines; sulfonated phthalocyanine complexes (containing mixtures of differently substituted derivatives) of Al (AlPcSmix), Zn (ZnPcSmix), Ge (GePcSmix), Si (SiPcSmix) and Sn (SnPcSmix). Photolysis of the chlorophenols resulted mainly in the formation of chlorobenzoquinone derivatives. The complexes showed order of activity towards the transformation of pentachlorophenol as follows: ZnOCPc > SiPcSmix > SnPcSmix > ZnPcSmix > GePcSmix > ZnPcS4 > AlPcSmix > AlOCPc > AlPcS4. The generation of singlet oxygen (1O2) by these immobilized MPc photosensitizers was found to play a major role in their photoactivities towards the transformation of these chlorophenols. Langmuir–Hinshelwood (L–H) kinetic model studies showed that the ZnOCPc, GePcSmix and ZnPcSmix photocatalysis occurred on the catalysts surface. © 2005 Elsevier B.V. All rights reserved.
- Full Text:
- Date Issued: 2006
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286043 , vital:56233 , xlink:href="https://doi.org/10.1016/j.molcata.2005.12.009"
- Description: Photolysis of aqueous solutions of chlorophenols (4-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and pentachlorophenol) in the presence of immobilized non-transition metal phthalocyanine photosensitizers onto Amberlite® is presented. The photosensitizers studied are: Al (AlOCPc) and Zn (ZnOCPc) octacarboxyphthalocyanines; Al (AlPcS4) and Zn (ZnPcS4) tetrasulfophthalocyanines; sulfonated phthalocyanine complexes (containing mixtures of differently substituted derivatives) of Al (AlPcSmix), Zn (ZnPcSmix), Ge (GePcSmix), Si (SiPcSmix) and Sn (SnPcSmix). Photolysis of the chlorophenols resulted mainly in the formation of chlorobenzoquinone derivatives. The complexes showed order of activity towards the transformation of pentachlorophenol as follows: ZnOCPc > SiPcSmix > SnPcSmix > ZnPcSmix > GePcSmix > ZnPcS4 > AlPcSmix > AlOCPc > AlPcS4. The generation of singlet oxygen (1O2) by these immobilized MPc photosensitizers was found to play a major role in their photoactivities towards the transformation of these chlorophenols. Langmuir–Hinshelwood (L–H) kinetic model studies showed that the ZnOCPc, GePcSmix and ZnPcSmix photocatalysis occurred on the catalysts surface. © 2005 Elsevier B.V. All rights reserved.
- Full Text:
- Date Issued: 2006
Novel amperometric glucose biosensor based on an ether-linked cobalt(II) phthalocyaninecobalt(II) tetraphenylporphyrin pentamer as a redox mediator
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6583 , http://hdl.handle.net/10962/d1004148
- Description: The development of cobalt(II) phthalocyanine–cobalt(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin), (CoPc–(CoTPP)[subscript 4]) pentamer as a novel redox mediator for amperometric enzyme electrode sensitive to glucose is described. A glassy carbon electrode (GCE) was first modified with the pentamer, then followed by the immobilization onto the GCE–CoPc–(CoTPP)[subscript 4] with glucose oxidase (GOx) through cross-linking with glutaraldehyde in the presence of bovine serum albumin (BSA) and Nafion® cation-exchange polymer. The proposed biosensor displayed good amperometric respose charateristics to glucose in pH 7.0 PBS solution; such as low overpotentials (+400 mV versus Ag|AgCl), very fast amperometric response time (~5 s), linear concentration range extended up to 11 mM, with 10 μM detection limit. The biosensor exhibited electrochemical Michaelis–Menten kinetics and showed an average apparent Michaelis–Menten constant (K′M) of 14.91 ± 0.46 mM over a storage period of 2 weeks.
- Full Text:
- Date Issued: 2006
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6583 , http://hdl.handle.net/10962/d1004148
- Description: The development of cobalt(II) phthalocyanine–cobalt(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin), (CoPc–(CoTPP)[subscript 4]) pentamer as a novel redox mediator for amperometric enzyme electrode sensitive to glucose is described. A glassy carbon electrode (GCE) was first modified with the pentamer, then followed by the immobilization onto the GCE–CoPc–(CoTPP)[subscript 4] with glucose oxidase (GOx) through cross-linking with glutaraldehyde in the presence of bovine serum albumin (BSA) and Nafion® cation-exchange polymer. The proposed biosensor displayed good amperometric respose charateristics to glucose in pH 7.0 PBS solution; such as low overpotentials (+400 mV versus Ag|AgCl), very fast amperometric response time (~5 s), linear concentration range extended up to 11 mM, with 10 μM detection limit. The biosensor exhibited electrochemical Michaelis–Menten kinetics and showed an average apparent Michaelis–Menten constant (K′M) of 14.91 ± 0.46 mM over a storage period of 2 weeks.
- Full Text:
- Date Issued: 2006
Electrocatalysis of asulam on cobalt phthalocyanine modified multi-walled carbon nanotubes immobilized on a basal plane pyrolytic graphite electrode
- Siswana, Msimelelo P, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Siswana, Msimelelo P , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6595 , http://hdl.handle.net/10962/d1004344
- Description: This work describes the electrochemical properties of cobalt tetra-aminophthalocyanine (CoTAPc) complex electropolymerized at the surface of multi-walled carbon nanotube (MWCNT) abrasively immobilized onto a basal plane pyrolytic graphite electrode (BPPGE). The constructed electrode displayed excellent electrocatalytic behaviour towards the oxidation of the herbicide, asulam, as evidenced by the enhancement of the oxidation peak current (~6 times) and the shift in the oxidation potential to lower values (by ~120 mV) in comparison with the bare BPPGE. The chronoamperometric detection of asulam which was carried out in 0.10 M phosphate buffer (pH 7.0) at a fixed potential of 0.65 V (versus Ag|AgCl) yielded excellent analytical parameters; a linear concentration range of 4.5–20 μM, a sensitivity of 241 × 10[superscript −3] μA/μM, a detection limit of 1.15 μM asulam (using the Y[subscript B] + 3σ criterion) and a response time of ~2 s.
- Full Text:
- Date Issued: 2006
- Authors: Siswana, Msimelelo P , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6595 , http://hdl.handle.net/10962/d1004344
- Description: This work describes the electrochemical properties of cobalt tetra-aminophthalocyanine (CoTAPc) complex electropolymerized at the surface of multi-walled carbon nanotube (MWCNT) abrasively immobilized onto a basal plane pyrolytic graphite electrode (BPPGE). The constructed electrode displayed excellent electrocatalytic behaviour towards the oxidation of the herbicide, asulam, as evidenced by the enhancement of the oxidation peak current (~6 times) and the shift in the oxidation potential to lower values (by ~120 mV) in comparison with the bare BPPGE. The chronoamperometric detection of asulam which was carried out in 0.10 M phosphate buffer (pH 7.0) at a fixed potential of 0.65 V (versus Ag|AgCl) yielded excellent analytical parameters; a linear concentration range of 4.5–20 μM, a sensitivity of 241 × 10[superscript −3] μA/μM, a detection limit of 1.15 μM asulam (using the Y[subscript B] + 3σ criterion) and a response time of ~2 s.
- Full Text:
- Date Issued: 2006
Electropolymerizable iron (III) and cobalt (II) dicyanophenoxy tetraphenylporphyrin complexes
- Ozoemena, Kenneth I, Zhao, Zhixin, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Zhao, Zhixin , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286080 , vital:56236 , xlink:href="https://doi.org/10.1016/j.inoche.2005.11.024"
- Description: Solution and solid phase electrochemical features of 5-[4-(3,4-dicyanophenoxy)phenyl],10,15,20-triphenylporphyrin complexes of iron(III) (FeCNOTPP(Cl)) and cobalt(II) (CoCNOTPP) have been described. These novel asymmetric dicyanophenoxy-derivatised cobalt and iron porphyrin complexes were electropolymerised onto glassy carbon electrodes, which in aqueous solutions, gave surface concentrations (ca. 10−10 mol cm−2) typical of monolayer coverages. The films also exhibited excellent stability and electrocatalysis towards the direct detection of important analytes as nitrite, nitric oxide, and hydrogen peroxide in aqueous solutions.
- Full Text:
- Date Issued: 2006
- Authors: Ozoemena, Kenneth I , Zhao, Zhixin , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286080 , vital:56236 , xlink:href="https://doi.org/10.1016/j.inoche.2005.11.024"
- Description: Solution and solid phase electrochemical features of 5-[4-(3,4-dicyanophenoxy)phenyl],10,15,20-triphenylporphyrin complexes of iron(III) (FeCNOTPP(Cl)) and cobalt(II) (CoCNOTPP) have been described. These novel asymmetric dicyanophenoxy-derivatised cobalt and iron porphyrin complexes were electropolymerised onto glassy carbon electrodes, which in aqueous solutions, gave surface concentrations (ca. 10−10 mol cm−2) typical of monolayer coverages. The films also exhibited excellent stability and electrocatalysis towards the direct detection of important analytes as nitrite, nitric oxide, and hydrogen peroxide in aqueous solutions.
- Full Text:
- Date Issued: 2006
Synthesis and electrochemical characterisation of benzylmercapto and dodecylmercapto tetra substituted cobalt, iron, and zinc phthalocyanines complexes
- Nyokong, Tebello, Ozoemena, Kenneth I, Agboola, Bolade O
- Authors: Nyokong, Tebello , Ozoemena, Kenneth I , Agboola, Bolade O
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6580 , http://hdl.handle.net/10962/d1004143
- Description: The work reports on cyclic voltammetry (CV), square wave voltammetry and spectroelectrochemistry of the following complexes: tetrakis (benzyl mercapto) phthalocyanine complexes of Zn(II) (ZnTBMPc, 4a ), Co(II) (CoTBMPc, 5a ), Fe(II) (FeTBMPc 6a ); and tetrakis (dodecylmercapto) phthalocyanine complexes of Zn(II) (ZnTDMPc, 4b), Co(II) (CoTDMPc, 5b) and Fe(II) (FeTDMPc, 6b). More reversible CV couples were observed for complexes 4a, 5a and 6a containing thiol phenyl ring substituents. Complexes 4b, 5b and 6b containing long chain thiol substituents showed less reversible couples. Complexes 6a and 6b showed a relatively large number of redox processes (5 for 6a and 6 for 6b) within the potential window employed in this work. The processes for FePc derivatives (6a) are assigned to FeIIIPc-1/FeIIIPc-2, FeIIIPc-2/FeIIPc-2, FeIIPc-2/FeIPc-2, FeIPc-2/FeIPc-3 and FeIPc-3/FeIPc-4 and for the CoPc derivative (5a) to CoIIIPc-1/CoIIIPc-2, CoIIIPc-2/CoIIPc-2, CoIIPc-2/CoIPc-2 and CoIPc-2/CoIPc-3.
- Full Text:
- Date Issued: 2006
- Authors: Nyokong, Tebello , Ozoemena, Kenneth I , Agboola, Bolade O
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6580 , http://hdl.handle.net/10962/d1004143
- Description: The work reports on cyclic voltammetry (CV), square wave voltammetry and spectroelectrochemistry of the following complexes: tetrakis (benzyl mercapto) phthalocyanine complexes of Zn(II) (ZnTBMPc, 4a ), Co(II) (CoTBMPc, 5a ), Fe(II) (FeTBMPc 6a ); and tetrakis (dodecylmercapto) phthalocyanine complexes of Zn(II) (ZnTDMPc, 4b), Co(II) (CoTDMPc, 5b) and Fe(II) (FeTDMPc, 6b). More reversible CV couples were observed for complexes 4a, 5a and 6a containing thiol phenyl ring substituents. Complexes 4b, 5b and 6b containing long chain thiol substituents showed less reversible couples. Complexes 6a and 6b showed a relatively large number of redox processes (5 for 6a and 6 for 6b) within the potential window employed in this work. The processes for FePc derivatives (6a) are assigned to FeIIIPc-1/FeIIIPc-2, FeIIIPc-2/FeIIPc-2, FeIIPc-2/FeIPc-2, FeIPc-2/FeIPc-3 and FeIPc-3/FeIPc-4 and for the CoPc derivative (5a) to CoIIIPc-1/CoIIIPc-2, CoIIIPc-2/CoIIPc-2, CoIIPc-2/CoIPc-2 and CoIPc-2/CoIPc-3.
- Full Text:
- Date Issued: 2006
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
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
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
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
Preferential electrosorption of cobalt (II) tetra-aminophthalocyanine at single-wall carbon nanotubes immobilized on a basal plane pyrolytic graphite electrode
- Ozoemena, Kenneth I, Pillay, J, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Pillay, J , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6584 , http://hdl.handle.net/10962/d1004160
- Description: This communication describes the preferential electrosorption of cobalt (II) tetra-aminophthalocyanine (CoTAPc) (rather than the expected electropolymerisation) onto a SWCNT immobilized on a basal plane pyrolytic graphite electrode (BPPGE). Cyclic voltammetric and electrochemical impedance spectroscopic data revealed that the electrosorbed CoTAPc is highly stable, well organized with comparable electron-transfer rate constant in ferricyanide solution (k[subscript app] ~ 6 × 10[superscript (−5)] cm s[superscript (−1)] order) to that of the SWNCT. Electrochemical kinetics of the electrosorbed CoTAPc yielded k[subscript s] of 0.169 s[superscript (−1)] and 832.2 s[superscript (−1)] for the cathodic and anodic reactions, respectively, indicative of different rate-determining steps for the cathodic and anodic reactions. Strong π-stacking interactions between CoTAPc and the sidewalls of the SWCNTs, with possible synergistic covalent interactions, are explained as responsible for the preferential electrosorption process. Both BPPGE-SWCNT-CoTAPc[subscript (ads)] and BPPGE-SWCNT showed comparable electrocatalytic responses towards the detection of 2-(diethylamino) ethanethiol (DEAET).
- Full Text:
- Date Issued: 2006
- Authors: Ozoemena, Kenneth I , Pillay, J , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6584 , http://hdl.handle.net/10962/d1004160
- Description: This communication describes the preferential electrosorption of cobalt (II) tetra-aminophthalocyanine (CoTAPc) (rather than the expected electropolymerisation) onto a SWCNT immobilized on a basal plane pyrolytic graphite electrode (BPPGE). Cyclic voltammetric and electrochemical impedance spectroscopic data revealed that the electrosorbed CoTAPc is highly stable, well organized with comparable electron-transfer rate constant in ferricyanide solution (k[subscript app] ~ 6 × 10[superscript (−5)] cm s[superscript (−1)] order) to that of the SWNCT. Electrochemical kinetics of the electrosorbed CoTAPc yielded k[subscript s] of 0.169 s[superscript (−1)] and 832.2 s[superscript (−1)] for the cathodic and anodic reactions, respectively, indicative of different rate-determining steps for the cathodic and anodic reactions. Strong π-stacking interactions between CoTAPc and the sidewalls of the SWCNTs, with possible synergistic covalent interactions, are explained as responsible for the preferential electrosorption process. Both BPPGE-SWCNT-CoTAPc[subscript (ads)] and BPPGE-SWCNT showed comparable electrocatalytic responses towards the detection of 2-(diethylamino) ethanethiol (DEAET).
- Full Text:
- Date Issued: 2006
Comparative electrochemistry and electrocatalytic activities of cobalt, iron and manganese phthalocyanine complexes axially co-ordinated to mercaptopyridine self-assembled monolayer at gold electrodes
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286054 , vital:56234 , xlink:href="https://doi.org/10.1016/j.electacta.2005.08.007"
- Description: Comparative surface electrochemistry and electrocatalytic properties of solid ultrathin monolayer films of metallophthalocyanine (MPc) complexes of cobalt (CoPc), iron (FePc) and manganese (MnPc) self-immobilised, via axial ligation reaction, onto preformed 4-mercaptopyridine self-assembled monolayers (SAMs) on gold electrodes have been described. Surface electrochemical parameters of the modified electrodes showed that these MPc-SAMs are densely packed with flat orientations. The electrochemical, electrocatalytic and stability properties of these MPc complexes follow this order: FePc > MnPc > CoPc. This finding is remarkable as it suggests that the success of using this method of self-assembling of MPc onto gold electrode is largely dependent on the bond distance between the pyridine linker and the central metal of the MPc; the shorter the distance, the faster the co-ordination and the better the electrocatalytic properties towards L-cysteine and thiocyanate. Thus, the superiority of FePc-based SAM over those of the MnPc and CoPc, has been proposed to be the result of the more favorable axial co-ordination properties of FePc with pyridine (i.e. shorter Fe–N(pyridine) bond length.
- Full Text:
- Date Issued: 2006
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286054 , vital:56234 , xlink:href="https://doi.org/10.1016/j.electacta.2005.08.007"
- Description: Comparative surface electrochemistry and electrocatalytic properties of solid ultrathin monolayer films of metallophthalocyanine (MPc) complexes of cobalt (CoPc), iron (FePc) and manganese (MnPc) self-immobilised, via axial ligation reaction, onto preformed 4-mercaptopyridine self-assembled monolayers (SAMs) on gold electrodes have been described. Surface electrochemical parameters of the modified electrodes showed that these MPc-SAMs are densely packed with flat orientations. The electrochemical, electrocatalytic and stability properties of these MPc complexes follow this order: FePc > MnPc > CoPc. This finding is remarkable as it suggests that the success of using this method of self-assembling of MPc onto gold electrode is largely dependent on the bond distance between the pyridine linker and the central metal of the MPc; the shorter the distance, the faster the co-ordination and the better the electrocatalytic properties towards L-cysteine and thiocyanate. Thus, the superiority of FePc-based SAM over those of the MnPc and CoPc, has been proposed to be the result of the more favorable axial co-ordination properties of FePc with pyridine (i.e. shorter Fe–N(pyridine) bond length.
- Full Text:
- Date Issued: 2006
Electrocatalytic behaviour of carbon paste electrode modified with iron(II) phthalocyanine (FePc) nanoparticles towards the detection of amitrole
- Siswana, Msimelelo P, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Siswana, Msimelelo P , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6591 , http://hdl.handle.net/10962/d1004340
- Description: This paper describes the construction of a carbon paste electrode (CPE) impregnated with nanoparticles of iron(II) phthalocyanine (nanoFePc). The new electrode (nanoFePc-CPE) revealed interesting electrocatalytic behaviour towards amitrole; pure catalytic diffusion-controlled process, with high Tafel slope (235 mV/decade) suggesting strong binding of amitrole with nanoFePc catalyst. The effects of catalyst loading, varying pH and electrolytes were studied. The mechanism for the interaction of amitrole with the nanoFePc is proposed to involve the Fe[superscript (III)]Pc/Fe[superscript (II)]Pc redox process. Using chronoamperometry (E = +0.42 V versus Ag/AgCl) technique, the sensor was reliably employed for amitrole assay at pH 12.0 phosphate buffer (with sodium sulphate as the supporting electrolyte) for up to 12 nM amitrole with excellent sensitivity (ca. 3.44 μA/nM) and low detection limit (3.62 ± 0.11 nM, i.e. 0.305 μg L[superscript (−1)] using the YB + 3σB criterion and 0.85 ± 0.03 nM, i.e. 70 ng/L with the Y[subscript B] + 2[subscript σB] criterion) as well as satisfactory amperometric selectivity coefficient (K[subscript amp] ≈ 7.4 × 10[superscript (−4)] for ammonium thiocyanate, a component of many amitrole herbicides, and 3.2 × 10[superscript (−3)] for asulam pesticide). The surface of the electrode can easily be regenerated by simple polishing on an alumina paper, obtaining a fresh surface ready for use in a new assay. The proposed electrode was successfully applied in the quantification of amitrole in its commercial formulation as well as in tap water samples.
- Full Text:
- Date Issued: 2006
- Authors: Siswana, Msimelelo P , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6591 , http://hdl.handle.net/10962/d1004340
- Description: This paper describes the construction of a carbon paste electrode (CPE) impregnated with nanoparticles of iron(II) phthalocyanine (nanoFePc). The new electrode (nanoFePc-CPE) revealed interesting electrocatalytic behaviour towards amitrole; pure catalytic diffusion-controlled process, with high Tafel slope (235 mV/decade) suggesting strong binding of amitrole with nanoFePc catalyst. The effects of catalyst loading, varying pH and electrolytes were studied. The mechanism for the interaction of amitrole with the nanoFePc is proposed to involve the Fe[superscript (III)]Pc/Fe[superscript (II)]Pc redox process. Using chronoamperometry (E = +0.42 V versus Ag/AgCl) technique, the sensor was reliably employed for amitrole assay at pH 12.0 phosphate buffer (with sodium sulphate as the supporting electrolyte) for up to 12 nM amitrole with excellent sensitivity (ca. 3.44 μA/nM) and low detection limit (3.62 ± 0.11 nM, i.e. 0.305 μg L[superscript (−1)] using the YB + 3σB criterion and 0.85 ± 0.03 nM, i.e. 70 ng/L with the Y[subscript B] + 2[subscript σB] criterion) as well as satisfactory amperometric selectivity coefficient (K[subscript amp] ≈ 7.4 × 10[superscript (−4)] for ammonium thiocyanate, a component of many amitrole herbicides, and 3.2 × 10[superscript (−3)] for asulam pesticide). The surface of the electrode can easily be regenerated by simple polishing on an alumina paper, obtaining a fresh surface ready for use in a new assay. The proposed electrode was successfully applied in the quantification of amitrole in its commercial formulation as well as in tap water samples.
- Full Text:
- Date Issued: 2006
Self-assembled monolayers (SAMs) of cobalt tetracarboxylic acidchloride phthalocyanine covalently attached onto a preformed mercaptoethanol SAM
- Mashazi, Philani N, Ozoemena, Kenneth I, Maree, David M, Nyokong, Tebello
- Authors: Mashazi, Philani N , Ozoemena, Kenneth I , Maree, David M , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283792 , vital:55989 , xlink:href="https://doi.org/10.1016/j.electacta.2005.10.004"
- Description: A feasible method of fabricating phthalocyanine sensor was developed by covalent attachment of cobalt tetracarboxylic acidchloride phthalocyanine (CoTCACIPc) onto a preformed 2-mercaptoethanol (2-ME) self-assembled monolayer (SAM) modified gold electrode (designated as CoTCACIPc-2-ME-SAM). The surface concentration of the CoTCACIPc was found to be 4.58 × 10−10 mol/cm2. The sensor gave a linear response to L-cysteine over the concentration range 0.28–20 μM with a detection limit of 5 × 10−7 M and best response time of 2 s.
- Full Text:
- Date Issued: 2006
- Authors: Mashazi, Philani N , Ozoemena, Kenneth I , Maree, David M , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283792 , vital:55989 , xlink:href="https://doi.org/10.1016/j.electacta.2005.10.004"
- Description: A feasible method of fabricating phthalocyanine sensor was developed by covalent attachment of cobalt tetracarboxylic acidchloride phthalocyanine (CoTCACIPc) onto a preformed 2-mercaptoethanol (2-ME) self-assembled monolayer (SAM) modified gold electrode (designated as CoTCACIPc-2-ME-SAM). The surface concentration of the CoTCACIPc was found to be 4.58 × 10−10 mol/cm2. The sensor gave a linear response to L-cysteine over the concentration range 0.28–20 μM with a detection limit of 5 × 10−7 M and best response time of 2 s.
- Full Text:
- Date Issued: 2006
Electrochemical properties of benzylmercapto and dodecylmercapto tetra substituted nickel phthalocyanine complexes: Electrocatalytic oxidation of nitrite
- Agboola, Bolade O, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Agboola, Bolade O , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6562 , http://hdl.handle.net/10962/d1003826
- Description: Nickel tetrakis(benzylmercapto)phthalocyanine (NiTBMPc) and nickel tetrakis(dodecylmercapto)phthalocyanine (NiTDMPc) complexes were synthesized and their spectral and electrochemical properties reported. The CV showed four or five redox processes for NiTBMPc and NiTDMPc, respectively. For the first time, spectroelectrochemistry gave evidence for the formation of NiII/NiI process in a NiPc complex. The rest of the processes were ring based. The NiTBMPc complex was successfully deposited on both gold and glassy carbon electrodes by electropolymerisation while NiTDMPc complex was deposited on gold electrode only. The films were electro-transformed in aqueous 0.1 M NaOH solution to the O–Ni–O oxo bridged form. The modified electrodes were characterized using electrochemical impedance spectroscopy and the results showed typical behavior for modified electrodes. Electrodes with poly-Ni(OH)Pcs films exhibited higher charge transfer resistance values, Rp than their corresponding poly-NiPcs films counterparts. All the modified electrodes showed improved catalytic activities than the unmodified electrodes towards nitrite ions electrooxidation. Better catalytic activities were observed for the modified electrodes when they were transformed to O–Ni–O oxo bridge form. All the modified electrodes exhibited high resistance to electrode surface passivation.
- Full Text:
- Date Issued: 2006
- Authors: Agboola, Bolade O , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6562 , http://hdl.handle.net/10962/d1003826
- Description: Nickel tetrakis(benzylmercapto)phthalocyanine (NiTBMPc) and nickel tetrakis(dodecylmercapto)phthalocyanine (NiTDMPc) complexes were synthesized and their spectral and electrochemical properties reported. The CV showed four or five redox processes for NiTBMPc and NiTDMPc, respectively. For the first time, spectroelectrochemistry gave evidence for the formation of NiII/NiI process in a NiPc complex. The rest of the processes were ring based. The NiTBMPc complex was successfully deposited on both gold and glassy carbon electrodes by electropolymerisation while NiTDMPc complex was deposited on gold electrode only. The films were electro-transformed in aqueous 0.1 M NaOH solution to the O–Ni–O oxo bridged form. The modified electrodes were characterized using electrochemical impedance spectroscopy and the results showed typical behavior for modified electrodes. Electrodes with poly-Ni(OH)Pcs films exhibited higher charge transfer resistance values, Rp than their corresponding poly-NiPcs films counterparts. All the modified electrodes showed improved catalytic activities than the unmodified electrodes towards nitrite ions electrooxidation. Better catalytic activities were observed for the modified electrodes when they were transformed to O–Ni–O oxo bridge form. All the modified electrodes exhibited high resistance to electrode surface passivation.
- Full Text:
- Date Issued: 2006
Synthesis and electrochemical properties of benzyl-mercapto and dodecyl-mercapto tetrasubstituted manganese phthalocyanine complexes
- Agboola, Bolade, Ozoemena, Kenneth I, Westbroek, Philippe, Nyokong, Tebello
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Westbroek, Philippe , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281321 , vital:55713 , xlink:href="https://doi.org/10.1016/j.electacta.2006.09.002"
- Description: Manganese tetrakis (benzyl-mercapto) phthalocyanine (MnTBMPc) and manganese tetrakis (dodecyl-mercapto) phthalocyanine (MnTDMPc) complexes were synthesized and their spectral and electrochemical properties are reported. Cyclic voltammetric data showed three reversible to quasi-reversible and two irreversible redox processes for both complexes. Ring substituents influenced the positions of both oxidation and reduction redox couples. Spectroelectrochemistry confirmed the first two reductions to be due to MnIIIPc2−/MnIIPc2− and MnIIPc3−/MnIIPc2− processes. The first example of a formation of self-assembled monolayers (SAMs) using thiol substituted MnPc complexes is presented, the SAMs were found to show blocking characteristics towards some faradaic reactions.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Westbroek, Philippe , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281321 , vital:55713 , xlink:href="https://doi.org/10.1016/j.electacta.2006.09.002"
- Description: Manganese tetrakis (benzyl-mercapto) phthalocyanine (MnTBMPc) and manganese tetrakis (dodecyl-mercapto) phthalocyanine (MnTDMPc) complexes were synthesized and their spectral and electrochemical properties are reported. Cyclic voltammetric data showed three reversible to quasi-reversible and two irreversible redox processes for both complexes. Ring substituents influenced the positions of both oxidation and reduction redox couples. Spectroelectrochemistry confirmed the first two reductions to be due to MnIIIPc2−/MnIIPc2− and MnIIPc3−/MnIIPc2− processes. The first example of a formation of self-assembled monolayers (SAMs) using thiol substituted MnPc complexes is presented, the SAMs were found to show blocking characteristics towards some faradaic reactions.
- Full Text:
- Date Issued: 2007
Electrocatalytic detection of amitrole on the multi-walled carbon nanotube–iron (II) tetra-aminophthalocyanine platform
- Siswana, Msimelelo P, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Siswana, Msimelelo P , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265924 , vital:53901 , xlink:href="https://doi.org/10.3390/s8085096"
- Description: It is shown that iron(II) tetra-aminophthalocyanine complex electropolymerized onto a multi-walled carbon nanotube-modified basal plane pyrolytic graphite electrode greatly enhanced the electrocatalytic detetion of amitrole (a toxic herbicide), resulting in a very low detection limit (0.5 nM) and excellent sensitivity of 8.80±0.44 μA/nM, compared to any known work reported so far. The electrocatalytic detection of amitrole at this electrode occurred at less positive potential (~0.3 V vs Ag|ACl) and also revealed a typical coupled chemical reaction. The mechanism for this response is proposed. The electrode gave satisfactory selectivity to amitrole in the presence of other potential interfering pesticides in aqueous solutions.
- Full Text:
- Date Issued: 2008
- Authors: Siswana, Msimelelo P , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265924 , vital:53901 , xlink:href="https://doi.org/10.3390/s8085096"
- Description: It is shown that iron(II) tetra-aminophthalocyanine complex electropolymerized onto a multi-walled carbon nanotube-modified basal plane pyrolytic graphite electrode greatly enhanced the electrocatalytic detetion of amitrole (a toxic herbicide), resulting in a very low detection limit (0.5 nM) and excellent sensitivity of 8.80±0.44 μA/nM, compared to any known work reported so far. The electrocatalytic detection of amitrole at this electrode occurred at less positive potential (~0.3 V vs Ag|ACl) and also revealed a typical coupled chemical reaction. The mechanism for this response is proposed. The electrode gave satisfactory selectivity to amitrole in the presence of other potential interfering pesticides in aqueous solutions.
- Full Text:
- Date Issued: 2008
Tuning the physico-electrochemical properties of novel cobalt (II) octa [(3, 5-biscarboxylate)-phenoxy] phthalocyanine complex using phenylamine-functionalised SWCNTs
- Agboola, Bolade O, Ozoemena, Kenneth I, Nyokong, Tebello, Fukuda, Takamitsu, Kobayashi, Nagao
- Authors: Agboola, Bolade O , Ozoemena, Kenneth I , Nyokong, Tebello , Fukuda, Takamitsu , Kobayashi, Nagao
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261692 , vital:53435 , xlink:href="https://doi.org/10.1016/j.carbon.2009.10.023"
- Description: The integration of phenylamine-functionalised SWCNTs (SWCNT-phenylamine) with a novel cobalt (II) octa[(3,5-biscarboxylate)-phenoxy] phthalocyanine (CoOBPPc) complex has been described. The physical and electrochemical properties of the CoOBPPc-SWCNT-phenylamine hybrid were evaluated using spectroscopy (IR and UV–vis), field emission scanning electron microscopy and electrochemistry (cyclic voltammetry and electrochemical impedance spectroscopy). Integration of SWCNT-phenylamine resulted in the physical transformation of the CoOBCPPc from the usually bluish colour of cobalt phthalocyanine complexes to a beautiful bright green colour. In addition, the heterogeneous electron transfer kinetics and electrocatalytic properties of the CoOBCPPc were greatly enhanced following the attachment of the SWCNT-phenylamine. The potential electrocatalytic application of the hybrid was tested using β-nicotinamide adenine dinucleotide (NADH) as a model biological analyte. Interestingly, the onset oxidation potential of this analyte was significantly reduced (300 mV) by this hybrid compared to the bare electrode.
- Full Text:
- Date Issued: 2010
- Authors: Agboola, Bolade O , Ozoemena, Kenneth I , Nyokong, Tebello , Fukuda, Takamitsu , Kobayashi, Nagao
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261692 , vital:53435 , xlink:href="https://doi.org/10.1016/j.carbon.2009.10.023"
- Description: The integration of phenylamine-functionalised SWCNTs (SWCNT-phenylamine) with a novel cobalt (II) octa[(3,5-biscarboxylate)-phenoxy] phthalocyanine (CoOBPPc) complex has been described. The physical and electrochemical properties of the CoOBPPc-SWCNT-phenylamine hybrid were evaluated using spectroscopy (IR and UV–vis), field emission scanning electron microscopy and electrochemistry (cyclic voltammetry and electrochemical impedance spectroscopy). Integration of SWCNT-phenylamine resulted in the physical transformation of the CoOBCPPc from the usually bluish colour of cobalt phthalocyanine complexes to a beautiful bright green colour. In addition, the heterogeneous electron transfer kinetics and electrocatalytic properties of the CoOBCPPc were greatly enhanced following the attachment of the SWCNT-phenylamine. The potential electrocatalytic application of the hybrid was tested using β-nicotinamide adenine dinucleotide (NADH) as a model biological analyte. Interestingly, the onset oxidation potential of this analyte was significantly reduced (300 mV) by this hybrid compared to the bare electrode.
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- Date Issued: 2010