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
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
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
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
Self-Assembled Monolayers of Cobalt and Iron Phthalocyanine Complexes on Gold Electrodes
- Ozoemena, Kenneth I, Nyokong, Tebello, Westbroek, Philippe
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello , Westbroek, Philippe
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290363 , vital:56743 , xlink:href="https://doi.org/10.1002/elan.200302753"
- Description: The self-assembling of the octa(hydroxyethylthio)-metallophthalocyanine {MOHETPc (M=Co and Fe)} complexes and their similar analogues, octabutylthiometallophthalocyanine {MOBTPc (M=Co and Fe)} complexes on gold electrodes are investigated. Comparative surface voltammetric insights into their distinct self-assembling properties with respect to the passivation of Faradaic processes and surface coverages, including their solution electrochemistry, suggest different orientations and non-cleavage of their CS bonds. In the pH 2−9 range, the reversible [M(III)Pc(−2)]+ / [M(II)Pc(−2)] redox couples show potential shifts close to −59 mV / pH. The gold electrodes modified with the SAMs of these species show electrocatalytic activity towards the oxidation of thiols (L-cysteine, homocysteine and penicillamine) and thiocyanate in acidic media with detection limits in the region of 10−7–10−6 mol dm−3. These monolayers are stable and easily reproducible.
- Full Text:
- Date Issued: 2003
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello , Westbroek, Philippe
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290363 , vital:56743 , xlink:href="https://doi.org/10.1002/elan.200302753"
- Description: The self-assembling of the octa(hydroxyethylthio)-metallophthalocyanine {MOHETPc (M=Co and Fe)} complexes and their similar analogues, octabutylthiometallophthalocyanine {MOBTPc (M=Co and Fe)} complexes on gold electrodes are investigated. Comparative surface voltammetric insights into their distinct self-assembling properties with respect to the passivation of Faradaic processes and surface coverages, including their solution electrochemistry, suggest different orientations and non-cleavage of their CS bonds. In the pH 2−9 range, the reversible [M(III)Pc(−2)]+ / [M(II)Pc(−2)] redox couples show potential shifts close to −59 mV / pH. The gold electrodes modified with the SAMs of these species show electrocatalytic activity towards the oxidation of thiols (L-cysteine, homocysteine and penicillamine) and thiocyanate in acidic media with detection limits in the region of 10−7–10−6 mol dm−3. These monolayers are stable and easily reproducible.
- 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