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
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
Effects of substituents and solvents on the photochemical properties of zinc phthalocyanine complexes and their protonated derivatives
- Ogunsipe, Abimbola Olukayode, Nyokong, Tebello
- Authors: Ogunsipe, Abimbola Olukayode , Nyokong, Tebello
- Date: 2004
- Language: English
- Type: Article
- Identifier: vital:6585 , http://hdl.handle.net/10962/d1004161
- Description: Zinc phthalocyanine derivatives containing various ring substituents and axial ligands were studied with respect to the effect of substituents on protonation. Aggregation resulted in failure of some of the ZnPc derivatives to protonate. In fact addition of protonating agents to aggregated ZnPc derivatives resulted in increase in aggregation followed by slow degradation. Axial ligands were lost on protonation. Photobleaching, fluorescence and singlet oxygen quantum yields of the protonated derivatives were compared with those of the unprotonated derivatives. In all cases protonation decreases the singlet oxygen and fluorescence quantum yields. However, photobleaching quantum yields decreased (i.e. stability increased) for the protonated derivatives except when axial ligands were present, where protonation resulted in decrease in stability.
- Full Text:
- Date Issued: 2004
- Authors: Ogunsipe, Abimbola Olukayode , Nyokong, Tebello
- Date: 2004
- Language: English
- Type: Article
- Identifier: vital:6585 , http://hdl.handle.net/10962/d1004161
- Description: Zinc phthalocyanine derivatives containing various ring substituents and axial ligands were studied with respect to the effect of substituents on protonation. Aggregation resulted in failure of some of the ZnPc derivatives to protonate. In fact addition of protonating agents to aggregated ZnPc derivatives resulted in increase in aggregation followed by slow degradation. Axial ligands were lost on protonation. Photobleaching, fluorescence and singlet oxygen quantum yields of the protonated derivatives were compared with those of the unprotonated derivatives. In all cases protonation decreases the singlet oxygen and fluorescence quantum yields. However, photobleaching quantum yields decreased (i.e. stability increased) for the protonated derivatives except when axial ligands were present, where protonation resulted in decrease in stability.
- 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
Synthesis and photochemical studies of substituted adjacent binaphthalophthalocyanines
- Seotsanyana-Mokhosi, Itumeleng, Nyokong, Tebello
- Authors: Seotsanyana-Mokhosi, Itumeleng , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289883 , vital:56689 , xlink:href="https://doi.org/10.1142/S1088424604000568"
- Description: Adjacent phthalocyanines with a binaphthalo backbone and phenoxy substituents were synthesized and their photochemical properties were investigated. The adjacent phthalocyanines are the binaphthalophthalocyanines, with the phenoxy, 4-tert-butylphenoxy and the sulfophenoxy substituents, respectively and bis-binaphthalophthalocyanine which has an extended π conjugation system and larger singlet oxygen quantum yield compared to the other compounds. The presence of the phenoxy substituents as well as the binaphthalo bridge does not cause a marked difference on the fluorescing properties of these complexes when compared to zinc phthalocyanine. The binaphthalo backbone allowed the molecules to photoswitch during photolysis affording them very high photostability.
- Full Text:
- Date Issued: 2004
- Authors: Seotsanyana-Mokhosi, Itumeleng , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289883 , vital:56689 , xlink:href="https://doi.org/10.1142/S1088424604000568"
- Description: Adjacent phthalocyanines with a binaphthalo backbone and phenoxy substituents were synthesized and their photochemical properties were investigated. The adjacent phthalocyanines are the binaphthalophthalocyanines, with the phenoxy, 4-tert-butylphenoxy and the sulfophenoxy substituents, respectively and bis-binaphthalophthalocyanine which has an extended π conjugation system and larger singlet oxygen quantum yield compared to the other compounds. The presence of the phenoxy substituents as well as the binaphthalo bridge does not cause a marked difference on the fluorescing properties of these complexes when compared to zinc phthalocyanine. The binaphthalo backbone allowed the molecules to photoswitch during photolysis affording them very high photostability.
- Full Text:
- Date Issued: 2004
The renaissance in optical spectroscopy of phthalocyanines and other tetraazaporphyrins
- Nyokong, Tebello, Isago, Hiroaki
- Authors: Nyokong, Tebello , Isago, Hiroaki
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289388 , vital:56628 , xlink:href="https://doi.org/10.1142/S1088424604000453"
- Description: Spectral properties of metallophthalocyanines and other tetraazaporphyrins are governed mainly by the Q band which originates from the π-π* transitions within the ring. The position and intensity of the Q band is important in tailoring new phthalocyanine derivatives for particular applications. Aggregation, the nature of the central metal, π conjugation, symmetry of the molecules, and axial, peripheral or non-peripheral substitutions affect the spectra and hence the properties of the phthalocyanine molecule. This review gives a brief outline on how optical spectroscopy provides useful informations on molecular and electronic structures, chemistry and physics of phthalocyanines and other tetraazaporphyrins.
- Full Text:
- Date Issued: 2004
- Authors: Nyokong, Tebello , Isago, Hiroaki
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289388 , vital:56628 , xlink:href="https://doi.org/10.1142/S1088424604000453"
- Description: Spectral properties of metallophthalocyanines and other tetraazaporphyrins are governed mainly by the Q band which originates from the π-π* transitions within the ring. The position and intensity of the Q band is important in tailoring new phthalocyanine derivatives for particular applications. Aggregation, the nature of the central metal, π conjugation, symmetry of the molecules, and axial, peripheral or non-peripheral substitutions affect the spectra and hence the properties of the phthalocyanine molecule. This review gives a brief outline on how optical spectroscopy provides useful informations on molecular and electronic structures, chemistry and physics of phthalocyanines and other tetraazaporphyrins.
- 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
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