Synthesis and photophysical properties of a covalently linked porphyrin-phthalocyanine conjugate
- Zhao, Zhixin, Ogunsipe, Abimbola O, Maree, M David, Nyokong, Tebello
- Authors: Zhao, Zhixin , Ogunsipe, Abimbola O , Maree, M David , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300358 , vital:57922 , xlink:href="https://doi.org/10.1142/S1088424605000253"
- Description: The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)4), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)4 and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.
- Full Text:
- Date Issued: 2005
- Authors: Zhao, Zhixin , Ogunsipe, Abimbola O , Maree, M David , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300358 , vital:57922 , xlink:href="https://doi.org/10.1142/S1088424605000253"
- Description: The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)4), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)4 and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.
- Full Text:
- Date Issued: 2005
Synthesis, electrochemical and electrocatalytic behaviour of thiophene-appended cobalt, manganese and zinc phthalocyanine complexes
- Obirai, Joseph, Nyokong, Tebello
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286103 , vital:56238 , xlink:href="https://doi.org/10.1016/j.electacta.2005.03.024"
- Description: This work reports on the syntheses of new thiophene tetra substituted cobalt, manganese and zinc phthalocyanine (CoTETPc, (Cl)MnTETPc and ZnTETPc) complexes. The redox processes due to the thiophene substituent on the ring of the metallophthalocyanines (MPcs) were observed, in addition to Pc ring and metal (for Co and Mn complexes) based redox activity. The electrocatalytic activity of the CoTETPc complex adsorbed on glassy carbon electrode (GCE) by drop/dry-thermal annealing was investigated using L-cysteine. The modified electrode was stable to repetitive use without any signs of deactivation by oxidation products and was used to determine L-cysteine at concentrations between 0.0015 and 1 mM in pH 4 aqueous conditions.
- Full Text:
- Date Issued: 2005
- Authors: Obirai, Joseph , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286103 , vital:56238 , xlink:href="https://doi.org/10.1016/j.electacta.2005.03.024"
- Description: This work reports on the syntheses of new thiophene tetra substituted cobalt, manganese and zinc phthalocyanine (CoTETPc, (Cl)MnTETPc and ZnTETPc) complexes. The redox processes due to the thiophene substituent on the ring of the metallophthalocyanines (MPcs) were observed, in addition to Pc ring and metal (for Co and Mn complexes) based redox activity. The electrocatalytic activity of the CoTETPc complex adsorbed on glassy carbon electrode (GCE) by drop/dry-thermal annealing was investigated using L-cysteine. The modified electrode was stable to repetitive use without any signs of deactivation by oxidation products and was used to determine L-cysteine at concentrations between 0.0015 and 1 mM in pH 4 aqueous conditions.
- Full Text:
- Date Issued: 2005
Synthesis, photophysicochemical studies of adjacently tetrasubstituted binaphthalo-phthalocyanines
- Seotsanyana-Mokhosi, Itumeleng, Chen, Ji-Yao, Nyokong, Tebello
- Authors: Seotsanyana-Mokhosi, Itumeleng , Chen, Ji-Yao , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289294 , vital:56616 , xlink:href="https://doi.org/10.1142/S108842460500040X"
- Description: Adjacent binaphthalo-phthalocyanines tetra-substituted with phenoxy (4a), 4-carboxyphenoxy (4b) and 4-t-butylphenoxy (4c) groups, as well as the di-substituted 4-carboxyphenoxy (5b) have been synthesized and characterized. The photophysical and photochemical behavior of 4a-c, were compared with those of the corresponding di-substituted derivatives, (5a-c). The secondary substituents on the phenoxy ring have an influence on the aggregation of the molecules and hence on their photophysical properties. All of the complexes exhibit a relatively good conversion of energy from the triplet-excited state to the singlet oxygen. The less aggregated molecule (4c), has the highest singlet oxygen quantum yield. For all the molecules, fluorescence yields are low and they all have relatively shorter triplet lifetimes compared with the unsubstituted zinc phthalocyanine. Increasing the number of ring substituents on these rigid MPc complexes (from complexes 5 to 4) showed a general increase in the triplet state lifetimes and singlet oxygen quantum yields, and a decrease in stability.
- Full Text:
- Date Issued: 2005
- Authors: Seotsanyana-Mokhosi, Itumeleng , Chen, Ji-Yao , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289294 , vital:56616 , xlink:href="https://doi.org/10.1142/S108842460500040X"
- Description: Adjacent binaphthalo-phthalocyanines tetra-substituted with phenoxy (4a), 4-carboxyphenoxy (4b) and 4-t-butylphenoxy (4c) groups, as well as the di-substituted 4-carboxyphenoxy (5b) have been synthesized and characterized. The photophysical and photochemical behavior of 4a-c, were compared with those of the corresponding di-substituted derivatives, (5a-c). The secondary substituents on the phenoxy ring have an influence on the aggregation of the molecules and hence on their photophysical properties. All of the complexes exhibit a relatively good conversion of energy from the triplet-excited state to the singlet oxygen. The less aggregated molecule (4c), has the highest singlet oxygen quantum yield. For all the molecules, fluorescence yields are low and they all have relatively shorter triplet lifetimes compared with the unsubstituted zinc phthalocyanine. Increasing the number of ring substituents on these rigid MPc complexes (from complexes 5 to 4) showed a general increase in the triplet state lifetimes and singlet oxygen quantum yields, and a decrease in stability.
- Full Text:
- Date Issued: 2005
Synthesis, spectral and electrochemical characterization of mercaptopyrimidine-substituted cobalt, manganese and Zn (II) phthalocyanine complexes
- Authors: Obirai, J , Nyokong, Tebello
- Date: 2005
- Language: English
- Type: Article
- Identifier: vital:6973 , http://hdl.handle.net/10962/d1018958
- Description: A new family of thiol-derivatized metallophthalocyanine has been synthesized. The electrochemical behaviors of the complexes have been investigated. The modified glassy carbon electrode using the electropolymerized manganese complex (poly-MnTMPyrPc) was characterized in aqueous solution. The result indicates that the complexes are easier to electropolymerize in dichloromethane (DCM) than in dimethylformamide (DMF). The poly-MnTPyrPc-modified electrode showed pH dependence within the pH range studied (2–8). The cathodic wave of the electrode showed more pH dependence than the anodic wave. Poly-MnTPyrPc could catalyse the reduction of oxygen. , Original publication is available at http://doi:10.1016/j.electacta.2004.12.003
- Full Text: false
- Date Issued: 2005
- Authors: Obirai, J , Nyokong, Tebello
- Date: 2005
- Language: English
- Type: Article
- Identifier: vital:6973 , http://hdl.handle.net/10962/d1018958
- Description: A new family of thiol-derivatized metallophthalocyanine has been synthesized. The electrochemical behaviors of the complexes have been investigated. The modified glassy carbon electrode using the electropolymerized manganese complex (poly-MnTMPyrPc) was characterized in aqueous solution. The result indicates that the complexes are easier to electropolymerize in dichloromethane (DCM) than in dimethylformamide (DMF). The poly-MnTPyrPc-modified electrode showed pH dependence within the pH range studied (2–8). The cathodic wave of the electrode showed more pH dependence than the anodic wave. Poly-MnTPyrPc could catalyse the reduction of oxygen. , Original publication is available at http://doi:10.1016/j.electacta.2004.12.003
- Full Text: false
- Date Issued: 2005
The effect of structure on the electrochemical properties of 14 marine pyrroloquinoline metabolites
- Antunes, Edith M, Maree, Suzanne E, Nyokong, Tebello, Davies-Coleman, Michael T, Maree, M David
- Authors: Antunes, Edith M , Maree, Suzanne E , Nyokong, Tebello , Davies-Coleman, Michael T , Maree, M David
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286126 , vital:56242 , xlink:href="https://doi.org/10.3184/030823405775146915"
- Description: The electrochemical properties of 14 structurally related pyrroloquinoline metabolites (compounds 1–14) isolated from marine sponges were studied in pH-varied experiments using cyclic and square wave voltammetry. In general both substitution patterns and pH were observed to influence the reduction potentials of these molecules.
- Full Text:
- Date Issued: 2005
- Authors: Antunes, Edith M , Maree, Suzanne E , Nyokong, Tebello , Davies-Coleman, Michael T , Maree, M David
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286126 , vital:56242 , xlink:href="https://doi.org/10.3184/030823405775146915"
- Description: The electrochemical properties of 14 structurally related pyrroloquinoline metabolites (compounds 1–14) isolated from marine sponges were studied in pH-varied experiments using cyclic and square wave voltammetry. In general both substitution patterns and pH were observed to influence the reduction potentials of these molecules.
- Full Text:
- Date Issued: 2005
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
Electrochemical behavior and detection of dopamine and ascorbic acid at an iron (II) tetrasulfophthalocyanine modified carbon paste microelectrode
- Oni, Joshua, Westbroek, Philippe, Nyokong, Tebello
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290279 , vital:56735 , xlink:href="https://doi.org/10.1002/elan.200390104"
- Description: In this article the electrocatalytic behavior of an iron(II)tetrasulfophthalocyanine modified carbon paste microelectrode for the oxidation of dopamine (DA) and ascorbic acid (AA) is described. Although the oxidation potential of ascorbic acid is shifted by over 100 mV to more positive potentials, no peak separation could be obtained. This can be explained by the immediate homogeneous reduction of the oxidation product of dopamine by ascorbic acid in solution. However, this reaction induces a shift of the half-wave potential as a function of ratio of concentration of dopamine to ascorbic acid (cDA/cAA). Therefore it was possible to determine the cAA and cDA from this potential shift and the experimental peak current. Detection limits of 4.5±0.2×10−7 and 7.5±0.5×10−7 mol L−1 were obtained respectively for dopamine and ascorbic acid for cDA/cAA>0.01.
- Full Text:
- Date Issued: 2003
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290279 , vital:56735 , xlink:href="https://doi.org/10.1002/elan.200390104"
- Description: In this article the electrocatalytic behavior of an iron(II)tetrasulfophthalocyanine modified carbon paste microelectrode for the oxidation of dopamine (DA) and ascorbic acid (AA) is described. Although the oxidation potential of ascorbic acid is shifted by over 100 mV to more positive potentials, no peak separation could be obtained. This can be explained by the immediate homogeneous reduction of the oxidation product of dopamine by ascorbic acid in solution. However, this reaction induces a shift of the half-wave potential as a function of ratio of concentration of dopamine to ascorbic acid (cDA/cAA). Therefore it was possible to determine the cAA and cDA from this potential shift and the experimental peak current. Detection limits of 4.5±0.2×10−7 and 7.5±0.5×10−7 mol L−1 were obtained respectively for dopamine and ascorbic acid for cDA/cAA>0.01.
- Full Text:
- Date Issued: 2003
Electrochemical behaviour of thiol-derivatised zinc (II) phthalocyanine complexes and their self-immobilised films at gold electrodes
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290295 , vital:56737 , xlink:href="https://doi.org/10.1016/j.microc.2003.08.002"
- Description: Electrochemical properties of novel, peripherally substituted zinc phthalocyanine complex, octa(4-methylphenylthio-) phthalocyaninatozinc(II) [ZnPc(SC6H4CH3)8] (1a) in DMF solution are presented. This complex showed five quasi-reversible/reversible, diffusion-controlled redox couples. Solution voltammetry of 1a showed little contrast with that of its alkythiol-derivative, octabutylthiophthalocyaninatozinc(II) [ZnPc(SC4H9)8] (1b) in that both thiol-substituents tend to show electron-withdrawing influence on the phthalocyanine ligands; complex 1a showing easier reduction and more difficult to oxidation when compared to 1b and other alkyl derivatives. The voltammetric features of the solid ultrathin films of 1a and 1b, immobilized on gold electrodes via the self-assembling technique, are also presented. Interestingly, the self-assembled films are stable and reproducible and provide good suppression to the following Faradaic processes; gold surface oxidation, solution ion species and underpotential deposition (UPD) of copper.
- Full Text:
- Date Issued: 2003
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290295 , vital:56737 , xlink:href="https://doi.org/10.1016/j.microc.2003.08.002"
- Description: Electrochemical properties of novel, peripherally substituted zinc phthalocyanine complex, octa(4-methylphenylthio-) phthalocyaninatozinc(II) [ZnPc(SC6H4CH3)8] (1a) in DMF solution are presented. This complex showed five quasi-reversible/reversible, diffusion-controlled redox couples. Solution voltammetry of 1a showed little contrast with that of its alkythiol-derivative, octabutylthiophthalocyaninatozinc(II) [ZnPc(SC4H9)8] (1b) in that both thiol-substituents tend to show electron-withdrawing influence on the phthalocyanine ligands; complex 1a showing easier reduction and more difficult to oxidation when compared to 1b and other alkyl derivatives. The voltammetric features of the solid ultrathin films of 1a and 1b, immobilized on gold electrodes via the self-assembling technique, are also presented. Interestingly, the self-assembled films are stable and reproducible and provide good suppression to the following Faradaic processes; gold surface oxidation, solution ion species and underpotential deposition (UPD) of copper.
- Full Text:
- Date Issued: 2003
Indomethacin reduces lipid peroxidation in rat brain homogenate by binding Fe2+
- Anoopkumar-Dukie, Shailendra, Lack, Barbara, McPhail, Kerry L, Nyokong, Tebello, Lambat, Zaynab, Maharaj, Deepat, Daya, Santy
- Authors: Anoopkumar-Dukie, Shailendra , Lack, Barbara , McPhail, Kerry L , Nyokong, Tebello , Lambat, Zaynab , Maharaj, Deepat , Daya, Santy
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304763 , vital:58487 , xlink:href="https://doi.org/10.1023/A:1021958016928"
- Description: One of the hallmarks of Alzheimer's disease (AD) is the progressive degeneration of cholinergic neurons in the cerebral cortex and hippocampus. It is generally accepted that this neuronal degeneration is due to free-radical-induced damage. These free radicals attack vital structural components of the neurons. This implies that agents that reduce free radical generation could potentially delay the progression of AD. Free radical generation in the brain is assisted by the presence of iron, required by the Fenton reaction. Thus, agents that reduce iron availability for this reaction could potentially reduce free radical formation. Since non steroidal anti-inflammatory drugs (NSAIDS) have been shown to reduce the severity of AD, we investigated the possible mechanism by which indomethacin could afford neuroprotection. Our results show that indomethacin (1 mM) is able to reduce the iron-induced rise in lipid peroxidation in rat brain homogenates. In addition, our NMR data indicate that indomethacin binds the Fe2+/Fe3+ ion. This was confirmed by a study using UV/Vis spectrophotometry. The results imply that indomethacin provides a neuroprotective effect by binding to iron and thus making it unavailable for free radical production.
- Full Text:
- Date Issued: 2003
- Authors: Anoopkumar-Dukie, Shailendra , Lack, Barbara , McPhail, Kerry L , Nyokong, Tebello , Lambat, Zaynab , Maharaj, Deepat , Daya, Santy
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304763 , vital:58487 , xlink:href="https://doi.org/10.1023/A:1021958016928"
- Description: One of the hallmarks of Alzheimer's disease (AD) is the progressive degeneration of cholinergic neurons in the cerebral cortex and hippocampus. It is generally accepted that this neuronal degeneration is due to free-radical-induced damage. These free radicals attack vital structural components of the neurons. This implies that agents that reduce free radical generation could potentially delay the progression of AD. Free radical generation in the brain is assisted by the presence of iron, required by the Fenton reaction. Thus, agents that reduce iron availability for this reaction could potentially reduce free radical formation. Since non steroidal anti-inflammatory drugs (NSAIDS) have been shown to reduce the severity of AD, we investigated the possible mechanism by which indomethacin could afford neuroprotection. Our results show that indomethacin (1 mM) is able to reduce the iron-induced rise in lipid peroxidation in rat brain homogenates. In addition, our NMR data indicate that indomethacin binds the Fe2+/Fe3+ ion. This was confirmed by a study using UV/Vis spectrophotometry. The results imply that indomethacin provides a neuroprotective effect by binding to iron and thus making it unavailable for free radical production.
- Full Text:
- Date Issued: 2003
Influence of cyclodextrins on the fluorescence, photostability and singlet oxygen quantum yields of zinc phthalocyanine and naphthalocyanine complexes
- Tau, Prudence, Ogunsipe, Abimbola O, Maree, Suzanne, Maree, M David, Nyokong, Tebello
- Authors: Tau, Prudence , Ogunsipe, Abimbola O , Maree, Suzanne , Maree, M David , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304775 , vital:58488 , xlink:href="https://doi.org/10.1142/S1088424603000562"
- Description: The effects of formation of cyclodextrin inclusion complexes on the photochemical and photophysical properties of zinc phthalocyanine (ZnPc) and various peripherally substituted zinc phthalocyanines as well as zinc naphthalocyanine (ZnNPc) are investigated. The cyclodextrins employed were the hydroxypropyl-γ-cyclodextrin and unsubstituted β-cyclodextrin. Job's plots were employed to confirm the stoichiometry of the inclusion complexes and showed 2:1 and 4:1 (cyclodextrin:phthalocyanine) inclusion behavior. The phthalocyanine inclusion complexes showed larger singlet oxygen quantum yield (ϕΔ) values when compared to the free phthalocyanines before inclusion, for complexes 1 (zinc naphthalocyanine), 2 (zinc tetranitrophthalocyanine) and 4 (zinc tetra-tert-butylphenoxyphthalocyanine). The fluorescence quantum yields generally remained unchanged following inclusion.
- Full Text:
- Date Issued: 2003
- Authors: Tau, Prudence , Ogunsipe, Abimbola O , Maree, Suzanne , Maree, M David , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304775 , vital:58488 , xlink:href="https://doi.org/10.1142/S1088424603000562"
- Description: The effects of formation of cyclodextrin inclusion complexes on the photochemical and photophysical properties of zinc phthalocyanine (ZnPc) and various peripherally substituted zinc phthalocyanines as well as zinc naphthalocyanine (ZnNPc) are investigated. The cyclodextrins employed were the hydroxypropyl-γ-cyclodextrin and unsubstituted β-cyclodextrin. Job's plots were employed to confirm the stoichiometry of the inclusion complexes and showed 2:1 and 4:1 (cyclodextrin:phthalocyanine) inclusion behavior. The phthalocyanine inclusion complexes showed larger singlet oxygen quantum yield (ϕΔ) values when compared to the free phthalocyanines before inclusion, for complexes 1 (zinc naphthalocyanine), 2 (zinc tetranitrophthalocyanine) and 4 (zinc tetra-tert-butylphenoxyphthalocyanine). The fluorescence quantum yields generally remained unchanged following inclusion.
- Full Text:
- Date Issued: 2003
Photochemical studies of binuclear phenoxysubstituted phthalocyanines containing catecholate bridges
- Seotsanyana-Mokhosi, Itumeleng, Maree, Suzanne, Maree, M David, Nyokong, Tebello
- Authors: Seotsanyana-Mokhosi, Itumeleng , Maree, Suzanne , Maree, M David , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304808 , vital:58492 , xlink:href="https://doi.org/10.1142/S1088424603000239"
- Description: Binuclear ZnPc complexes covalently bridged by catechol units have been synthesized and their absorption and photochemical properties examined. The complexes studied are 1,2-bis-2',9',16',23'-triphenoxyphthalocyaninatozinc benzene (6a), 1,2-bis-2'-9',16',23'-tri-4-carboxyphe-noxyphthalocyaninatozinc benzene (6b), 1,2-bis-2',9',16',23'-tri-4-nitrophenoxyphthalocyaninato- zinc benzene (6c) and 1,2-bis-2'-9',16',23'-tri-4-tert-butylphenoxyphthalocyaninatozinc benzene (6d). Larger intramolecular coupling was observed for 6b and 6c, containing the carboxyphenoxy and nitrophenoxy substituents, respectively, than for 6a and 6d. A single Q band peak was observed for the fluorescence spectra of 6b and 6c, whereas, 6a and 6d showed a split Q band. The absence of the high energy fluorescence peaks corresponding to absorbance peaks in the 640 nm region, suggests that the intramolecular coupling is broken by excitation for complexes 6b and 6c.
- Full Text:
- Date Issued: 2003
Photochemical studies of binuclear phenoxysubstituted phthalocyanines containing catecholate bridges
- Authors: Seotsanyana-Mokhosi, Itumeleng , Maree, Suzanne , Maree, M David , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304808 , vital:58492 , xlink:href="https://doi.org/10.1142/S1088424603000239"
- Description: Binuclear ZnPc complexes covalently bridged by catechol units have been synthesized and their absorption and photochemical properties examined. The complexes studied are 1,2-bis-2',9',16',23'-triphenoxyphthalocyaninatozinc benzene (6a), 1,2-bis-2'-9',16',23'-tri-4-carboxyphe-noxyphthalocyaninatozinc benzene (6b), 1,2-bis-2',9',16',23'-tri-4-nitrophenoxyphthalocyaninato- zinc benzene (6c) and 1,2-bis-2'-9',16',23'-tri-4-tert-butylphenoxyphthalocyaninatozinc benzene (6d). Larger intramolecular coupling was observed for 6b and 6c, containing the carboxyphenoxy and nitrophenoxy substituents, respectively, than for 6a and 6d. A single Q band peak was observed for the fluorescence spectra of 6b and 6c, whereas, 6a and 6d showed a split Q band. The absence of the high energy fluorescence peaks corresponding to absorbance peaks in the 640 nm region, suggests that the intramolecular coupling is broken by excitation for complexes 6b and 6c.
- Full Text:
- Date Issued: 2003
Phthalocyanines and related complexes as electrocatalysts for the detection of nitric oxide
- Nyokong, Tebello, Vilakazi, Sibulelo
- Authors: Nyokong, Tebello , Vilakazi, Sibulelo
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290346 , vital:56741 , xlink:href="https://doi.org/10.1016/S0039-9140(03)00356-4"
- Description: Metallophthalocyanine (MPc) and metalloporphyrin complexes as well as some metalloproteins including myoglobin, hemoglobin, cyanocobalamin and cytochrome c catalyse the detection of nitric oxide (NO). The catalytic process often involve changes in the oxidation state of the catalyst. These complexes catalyse both the reduction and oxidation of NO. MPc complexes containing electroactive central metals such as CoPc and FePc generally show better catalytic activity towards the detection of NO than complexes containing electroinacive central metals. However, the involvement of ring based redox processes was confirmed for the homogenous NO catalysis using CoPc.
- Full Text:
- Date Issued: 2003
- Authors: Nyokong, Tebello , Vilakazi, Sibulelo
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290346 , vital:56741 , xlink:href="https://doi.org/10.1016/S0039-9140(03)00356-4"
- Description: Metallophthalocyanine (MPc) and metalloporphyrin complexes as well as some metalloproteins including myoglobin, hemoglobin, cyanocobalamin and cytochrome c catalyse the detection of nitric oxide (NO). The catalytic process often involve changes in the oxidation state of the catalyst. These complexes catalyse both the reduction and oxidation of NO. MPc complexes containing electroactive central metals such as CoPc and FePc generally show better catalytic activity towards the detection of NO than complexes containing electroinacive central metals. However, the involvement of ring based redox processes was confirmed for the homogenous NO catalysis using CoPc.
- Full Text:
- Date Issued: 2003
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