Behavior of Palladium Nanoparticles in the Absence or Presence of Cobalt Tetraaminophthalocyanine for the Electrooxidation of Hydrazine
- Maringa, Audacity, Nyokong, Tebello
- Authors: Maringa, Audacity , Nyokong, Tebello
- Date: 2014
- Language: English
- Type: Article
- Identifier: vital:7305 , http://hdl.handle.net/10962/d1020382
- Description: We report on the electrodeposition of palladium nanoparticles (PdNPs) on a glassy carbon electrode (GCE) and onto a poly-CoTAPc-GCE (CoTAPc=cobalt tetraamino phthalocyanine) surface. The electrodes are denoted as PdNPs-GCE and PdNPs/poly-CoTAPc-GCE, respectively. PdNPs/poly-CoTAPc-GCE showed the best activity for the oxidation of hydrazine at the lowest potential of −0.28 V and with the highest currents. The results were further supported by electrochemical impedance spectroscopy (EIS) which showed that there was less resistance to charge transfer for PdNPs/poly-CoTAPc-GCE compared to PdNPs-GCE. The catalytic rate constant for hydrazine oxidation was 6.12×108 cm3 mol−1 s−1 using PdNPs/poly-CoTAPc-GCE. , Original publication is available at http://dx.doi.org/10.1002/elan.201400028
- Full Text: false
- Date Issued: 2014
- Authors: Maringa, Audacity , Nyokong, Tebello
- Date: 2014
- Language: English
- Type: Article
- Identifier: vital:7305 , http://hdl.handle.net/10962/d1020382
- Description: We report on the electrodeposition of palladium nanoparticles (PdNPs) on a glassy carbon electrode (GCE) and onto a poly-CoTAPc-GCE (CoTAPc=cobalt tetraamino phthalocyanine) surface. The electrodes are denoted as PdNPs-GCE and PdNPs/poly-CoTAPc-GCE, respectively. PdNPs/poly-CoTAPc-GCE showed the best activity for the oxidation of hydrazine at the lowest potential of −0.28 V and with the highest currents. The results were further supported by electrochemical impedance spectroscopy (EIS) which showed that there was less resistance to charge transfer for PdNPs/poly-CoTAPc-GCE compared to PdNPs-GCE. The catalytic rate constant for hydrazine oxidation was 6.12×108 cm3 mol−1 s−1 using PdNPs/poly-CoTAPc-GCE. , Original publication is available at http://dx.doi.org/10.1002/elan.201400028
- Full Text: false
- Date Issued: 2014
Effects of pyrene on the photophysical and two-photon absorption-based nonlinear optical properties of indium(III) phthalocyanines
- Sanusi, Kayode, Nyokong, Tebello
- Authors: Sanusi, Kayode , Nyokong, Tebello
- Date: 2014
- Language: English
- Type: Article
- Identifier: vital:7314 , http://hdl.handle.net/10962/d1020540
- Description: Photophysical and two-photon-dependent nonlinear absorption properties of two chloroindium(III) phthalocyanines bearing pyrene units have been investigated. The tetra- (3) and the tri- (4) pyrene-substituted phthalocyanines exhibit strong triplet absorption with high triplet yields () of 0.79 and 0.83, respectively. The measured nonlinear optical data, such as the two photon absorption cross-sections, the third- and second-order nonlinearities were found to be comparable with those of literature, thus, making the compounds promising candidates for a broad range of nonlinear optical applications. , Original publication is available at http://dx.doi.org/10.1080/00958972.2014.959509
- Full Text: false
- Date Issued: 2014
- Authors: Sanusi, Kayode , Nyokong, Tebello
- Date: 2014
- Language: English
- Type: Article
- Identifier: vital:7314 , http://hdl.handle.net/10962/d1020540
- Description: Photophysical and two-photon-dependent nonlinear absorption properties of two chloroindium(III) phthalocyanines bearing pyrene units have been investigated. The tetra- (3) and the tri- (4) pyrene-substituted phthalocyanines exhibit strong triplet absorption with high triplet yields () of 0.79 and 0.83, respectively. The measured nonlinear optical data, such as the two photon absorption cross-sections, the third- and second-order nonlinearities were found to be comparable with those of literature, thus, making the compounds promising candidates for a broad range of nonlinear optical applications. , Original publication is available at http://dx.doi.org/10.1080/00958972.2014.959509
- Full Text: false
- Date Issued: 2014
Photophysical behavior of Zn aminophenoxy substituted phthalocyanine conjugates with carboxylic acid-coated silica nanoparticles: Effect of point of substitution
- Fashina, Adedayo, Antunes, Edith M, Nyokong, Tebello
- Authors: Fashina, Adedayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Language: English
- Type: Article
- Identifier: vital:7318 , http://hdl.handle.net/10962/d1020563 , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2014.04.034
- Description: This work reports on the grafting of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally and peripherally with a 4-amino phenoxy group. The phthalocyanine dyes have free amino groups, facilitating covalent attachment of the dyes on the silica surface via amide bond formation. The surface area of the functionalized silica nanoparticles increased on conjugation but the pore volumes were reduced. The phthalocyanine functionalized silica nanoparticles showed lower fluorescence quantum yields as well as shorter triplet lifetimes compared to the free phthalocyanines in dimethyl formamide. For the non-peripherally substituted phthalocyanines increases in triplet yield quantum yields, lifetimes, and singlet oxygen quantum yields were observed.
- Full Text: false
- Date Issued: 2014
- Authors: Fashina, Adedayo , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Language: English
- Type: Article
- Identifier: vital:7318 , http://hdl.handle.net/10962/d1020563 , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2014.04.034
- Description: This work reports on the grafting of silica nanoparticles with zinc phthalocyanine complexes tetra-substituted non-peripherally and peripherally with a 4-amino phenoxy group. The phthalocyanine dyes have free amino groups, facilitating covalent attachment of the dyes on the silica surface via amide bond formation. The surface area of the functionalized silica nanoparticles increased on conjugation but the pore volumes were reduced. The phthalocyanine functionalized silica nanoparticles showed lower fluorescence quantum yields as well as shorter triplet lifetimes compared to the free phthalocyanines in dimethyl formamide. For the non-peripherally substituted phthalocyanines increases in triplet yield quantum yields, lifetimes, and singlet oxygen quantum yields were observed.
- Full Text: false
- Date Issued: 2014
Curriculum Vitae of Prof Tebello Nyokong (OMB)
- Authors: Nyokong, Tebello
- Date: 2013
- Language: English
- Type: Article , text
- Identifier: vital:7233 , http://hdl.handle.net/10962/d1006180
- Description: Department of Science and Technology (DST) and National Research Foundation (NRF) Professor of Medicinal Chemistry and Nanotechnology and Distinguished Professor of Chemistry at Rhodes University.
- Full Text:
- Date Issued: 2013
- Authors: Nyokong, Tebello
- Date: 2013
- Language: English
- Type: Article , text
- Identifier: vital:7233 , http://hdl.handle.net/10962/d1006180
- Description: Department of Science and Technology (DST) and National Research Foundation (NRF) Professor of Medicinal Chemistry and Nanotechnology and Distinguished Professor of Chemistry at Rhodes University.
- Full Text:
- Date Issued: 2013
Like a bolt from the blue : phthalocyanines in biomedical optics
- Sekkat, N, Van den Berg, H, Nyokong, Tebello, Lange, N
- Authors: Sekkat, N , Van den Berg, H , Nyokong, Tebello , Lange, N
- Date: 2012
- Subjects: Biomedical optics Fluorescence diagnosis Phthalocyanines NIR dyes Photodynamic therapy
- Language: English
- Type: Article
- Identifier: vital:6597 , http://hdl.handle.net/10962/d1004346 , http://dx.doi.org/10.3390/molecules17010098
- Description: The purpose of this review is to compile preclinical and clinical results on phthalocyanines (Pcs) as photosensitizers (PS) for Photodynamic Therapy (PDT) and contrast agents for fluorescence imaging. Indeed, Pcs are excellent candidates in these fields due to their strong absorbance in the NIR region and high chemical and photo-stability. In particular, this is mostly relevant for their in vivo activation in deeper tissular regions. However, most Pcs present two major limitations, i.e., a strong tendency to aggregate and a low water-solubility. In order to overcome these issues, both chemical tuning and pharmaceutical formulation combined with tumor targeting strategies were applied. These aspects will be developed in this review for the most extensively studied Pcs during the last 25 years, i.e., aluminium-, zinc- and silicon-based Pcs.
- Full Text:
- Date Issued: 2012
- Authors: Sekkat, N , Van den Berg, H , Nyokong, Tebello , Lange, N
- Date: 2012
- Subjects: Biomedical optics Fluorescence diagnosis Phthalocyanines NIR dyes Photodynamic therapy
- Language: English
- Type: Article
- Identifier: vital:6597 , http://hdl.handle.net/10962/d1004346 , http://dx.doi.org/10.3390/molecules17010098
- Description: The purpose of this review is to compile preclinical and clinical results on phthalocyanines (Pcs) as photosensitizers (PS) for Photodynamic Therapy (PDT) and contrast agents for fluorescence imaging. Indeed, Pcs are excellent candidates in these fields due to their strong absorbance in the NIR region and high chemical and photo-stability. In particular, this is mostly relevant for their in vivo activation in deeper tissular regions. However, most Pcs present two major limitations, i.e., a strong tendency to aggregate and a low water-solubility. In order to overcome these issues, both chemical tuning and pharmaceutical formulation combined with tumor targeting strategies were applied. These aspects will be developed in this review for the most extensively studied Pcs during the last 25 years, i.e., aluminium-, zinc- and silicon-based Pcs.
- Full Text:
- Date Issued: 2012
Surface electrochemistry : structured electrode, synthesis, and characterization
- Bedioui, Fethi, Nyokong, Tebello, Zagal, Jose H
- Authors: Bedioui, Fethi , Nyokong, Tebello , Zagal, Jose H
- Date: 2012
- Language: English
- Type: Article
- Identifier: vital:6567 , http://hdl.handle.net/10962/d1004126 , http://dx.doi.org/10.1155/2012/405825
- Description: From introduction: The aim of this special issue is to show, through recent updated significant examples, how the electrochemical techniques allow the unique characterization of specific properties of micro- and nanostructured materials that offer varied possibilities of uses and the preparation of specific types of ordered materials that take advantage of electrochemical synthetic methods such as structuring nanosized wires and dots, to cite only two examples.
- Full Text:
- Date Issued: 2012
- Authors: Bedioui, Fethi , Nyokong, Tebello , Zagal, Jose H
- Date: 2012
- Language: English
- Type: Article
- Identifier: vital:6567 , http://hdl.handle.net/10962/d1004126 , http://dx.doi.org/10.1155/2012/405825
- Description: From introduction: The aim of this special issue is to show, through recent updated significant examples, how the electrochemical techniques allow the unique characterization of specific properties of micro- and nanostructured materials that offer varied possibilities of uses and the preparation of specific types of ordered materials that take advantage of electrochemical synthetic methods such as structuring nanosized wires and dots, to cite only two examples.
- Full Text:
- Date Issued: 2012
Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions
- Zagal, José H, Griveau, Sophie J, Silva, Francisco, Nyokong, Tebello, Bedioui, Fethi
- Authors: Zagal, José H , Griveau, Sophie J , Silva, Francisco , Nyokong, Tebello , Bedioui, Fethi
- Date: 2010
- Language: English
- Type: text , Article
- Identifier: vital:7239 , http://hdl.handle.net/10962/d1019718
- Description: Metallophthalocyanines confined on the surface of electrodes are active catalysts for a large variety of electrochemical reactions and electrode surfaces modified by these complexes can be obtained by simple adsorption on graphite and carbon. However, more stable electrodes can be achieved by coating their surfaces with electropolymerized layers of the complexes, that show similar activity than their monomer counterparts. In all cases, fundamental studies carried out with adsorbed layers of these complexes have shown that the redox potential is a very good reactivity index for predicting the catalytic activity of the complexes. Volcano-shaped correlations have been found between the electrocatalytic activity (as log I at constant E) versus the Co(II)/(I) formal potential (E°′) of Co-macrocyclics for the oxidation of several thiols, hydrazine and glucose. For the electroreduction of O2 only linear correlations between the electrocatalytic activity versus the M(III)/M(II) formal potential have been found using Cr, Mn, Fe and Co phthalocyanines but it is likely that these correlations are “incomplete volcano” correlations. The volcano correlations strongly suggest that E°′, the formal potential of the complex needs to be in a rather narrow potential window for achieving maximum activity, probably corresponding to surface coverages of an M-molecule adduct equal to 0.5 and to standard free energies of adsorption of the reacting molecule on the complex active site equal to zero. These results indicate that the catalytic activity of metallophthalocyanines for the oxidation of several molecules can be “tuned” by manipulating the E°′ formal potential, using proper groups on the macrocyclic ligand. This review emphasizes once more that metallophthalocyanines are extremely versatile materials with many applications in electrocatalysis, electroanalysis, just to mention a few, and they provide very good models for testing their catalytic activity for several reactions. Even though the earlier applications of these complexes were focused on providing active materials for electroreduction of O2, for making active cathodes for fuel cells, the main trend in the literature nowadays is to use these complexes for making active electrodes for electrochemical sensors. , Original publication is available at http://dx.doi.org/10.1016/j.ccr.2010.05.001
- Full Text: false
- Date Issued: 2010
- Authors: Zagal, José H , Griveau, Sophie J , Silva, Francisco , Nyokong, Tebello , Bedioui, Fethi
- Date: 2010
- Language: English
- Type: text , Article
- Identifier: vital:7239 , http://hdl.handle.net/10962/d1019718
- Description: Metallophthalocyanines confined on the surface of electrodes are active catalysts for a large variety of electrochemical reactions and electrode surfaces modified by these complexes can be obtained by simple adsorption on graphite and carbon. However, more stable electrodes can be achieved by coating their surfaces with electropolymerized layers of the complexes, that show similar activity than their monomer counterparts. In all cases, fundamental studies carried out with adsorbed layers of these complexes have shown that the redox potential is a very good reactivity index for predicting the catalytic activity of the complexes. Volcano-shaped correlations have been found between the electrocatalytic activity (as log I at constant E) versus the Co(II)/(I) formal potential (E°′) of Co-macrocyclics for the oxidation of several thiols, hydrazine and glucose. For the electroreduction of O2 only linear correlations between the electrocatalytic activity versus the M(III)/M(II) formal potential have been found using Cr, Mn, Fe and Co phthalocyanines but it is likely that these correlations are “incomplete volcano” correlations. The volcano correlations strongly suggest that E°′, the formal potential of the complex needs to be in a rather narrow potential window for achieving maximum activity, probably corresponding to surface coverages of an M-molecule adduct equal to 0.5 and to standard free energies of adsorption of the reacting molecule on the complex active site equal to zero. These results indicate that the catalytic activity of metallophthalocyanines for the oxidation of several molecules can be “tuned” by manipulating the E°′ formal potential, using proper groups on the macrocyclic ligand. This review emphasizes once more that metallophthalocyanines are extremely versatile materials with many applications in electrocatalysis, electroanalysis, just to mention a few, and they provide very good models for testing their catalytic activity for several reactions. Even though the earlier applications of these complexes were focused on providing active materials for electroreduction of O2, for making active cathodes for fuel cells, the main trend in the literature nowadays is to use these complexes for making active electrodes for electrochemical sensors. , Original publication is available at http://dx.doi.org/10.1016/j.ccr.2010.05.001
- Full Text: false
- Date Issued: 2010
The synthesis and photophysical properties of water soluble tetrasulfonated, octacarboxylated and quaternised 2,(3)-tetra-(2 pyridiloxy) Ga phthalocyanines
- Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2010
- Language: English
- Type: Article
- Identifier: vital:6579 , http://hdl.handle.net/10962/d1004142
- Description: The photophysical behaviour of chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine (ClGaT-2-PyPc) and its quaternised derivative were compared with that of the water soluble anionic tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydoxy gallium octacarboxy phthalocyanine ((OH)GaOCPc). Although both the quaternised compound and the tetrasulfonated gallium phthalocyanine aggregated in aq. solution at pH 11, resulting in low fluorescence and triplet yields, the presence of the surfactant Cremophore EL improved yields. Triplet quantum yields ranged from 0.52 to 0.70 and fluorescence quantum yields ranged from <0.01 to 0.21. The nature of substituent (sulfonate, carboxy and pyridiloxy) did not influence photophysical properties. Chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine and its quaternised derivative displayed longer triplet lifetime than both the tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydroxy gallium octacarboxy phthalocyanine in DMSO and in aq. media in both the presence and absence of surfactant.
- Full Text:
- Date Issued: 2010
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2010
- Language: English
- Type: Article
- Identifier: vital:6579 , http://hdl.handle.net/10962/d1004142
- Description: The photophysical behaviour of chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine (ClGaT-2-PyPc) and its quaternised derivative were compared with that of the water soluble anionic tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydoxy gallium octacarboxy phthalocyanine ((OH)GaOCPc). Although both the quaternised compound and the tetrasulfonated gallium phthalocyanine aggregated in aq. solution at pH 11, resulting in low fluorescence and triplet yields, the presence of the surfactant Cremophore EL improved yields. Triplet quantum yields ranged from 0.52 to 0.70 and fluorescence quantum yields ranged from <0.01 to 0.21. The nature of substituent (sulfonate, carboxy and pyridiloxy) did not influence photophysical properties. Chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine and its quaternised derivative displayed longer triplet lifetime than both the tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydroxy gallium octacarboxy phthalocyanine in DMSO and in aq. media in both the presence and absence of surfactant.
- Full Text:
- Date Issued: 2010
Fluorescence studies of quantum dots and zinc tetraamino phthalocyanine conjugates
- Britton, Jonathan, Antunes, Edith M, Nyokong, Tebello
- Authors: Britton, Jonathan , Antunes, Edith M , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6565 , http://hdl.handle.net/10962/d1004124
- Description: CdTe Qds capped with mercapto propionic acid (MPA) were covalently linked to zinc tetraamino phthalocyanine (ZnTAPc) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of the formation of an amide bond between ZnTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and a mixture of QDs and ZnTAPc (i.e. without chemical linking) showed Förster resonance energy transfer (FRET). ZnTAPc quenched the QDs emission, giving quenching constants in the order of 103 M−1.
- Full Text:
- Date Issued: 2009
- Authors: Britton, Jonathan , Antunes, Edith M , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6565 , http://hdl.handle.net/10962/d1004124
- Description: CdTe Qds capped with mercapto propionic acid (MPA) were covalently linked to zinc tetraamino phthalocyanine (ZnTAPc) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of the formation of an amide bond between ZnTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and a mixture of QDs and ZnTAPc (i.e. without chemical linking) showed Förster resonance energy transfer (FRET). ZnTAPc quenched the QDs emission, giving quenching constants in the order of 103 M−1.
- Full Text:
- Date Issued: 2009
New soluble methylendioxy-phenoxy-substituted zinc phthalocyanine derivatives : synthesis, photophysical and photochemical studies
- Erdoğmuş, Ali, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6572 , http://hdl.handle.net/10962/d1004135
- Description: The syntheses of new three phthalonitriles (1, 2 and 3), together with photophysical and photochemical properties of the resulting peripherally and non-peripherally tetrakis- and octakis 3,4-(methylendioxy)-phenoxy-substituted zinc phthalocyanines (4, 5 and 6) are described for the first time. Complexes 4, 5 and 6 have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. Complexes 4, 5 and 6 have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are mainly not aggregated (except for complex 6 in DMSO) within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO and toluene. Complex 4 has higher singlet oxygen quantum yields, fluorescence quantum yields, triplet quantum yields and triplet life times than complexes 5 and 6. The effect of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (4, 5 and 6) are also reported.
- Full Text:
- Date Issued: 2009
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6572 , http://hdl.handle.net/10962/d1004135
- Description: The syntheses of new three phthalonitriles (1, 2 and 3), together with photophysical and photochemical properties of the resulting peripherally and non-peripherally tetrakis- and octakis 3,4-(methylendioxy)-phenoxy-substituted zinc phthalocyanines (4, 5 and 6) are described for the first time. Complexes 4, 5 and 6 have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. Complexes 4, 5 and 6 have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are mainly not aggregated (except for complex 6 in DMSO) within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO and toluene. Complex 4 has higher singlet oxygen quantum yields, fluorescence quantum yields, triplet quantum yields and triplet life times than complexes 5 and 6. The effect of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (4, 5 and 6) are also reported.
- Full Text:
- Date Issued: 2009
Spectroscopic and photophysicochemical behaviour of novel cadmium phthalocyanine derivatives tetra-substituted at the alpha and beta positions
- Nyokong, Tebello, Chidawanyika, Wadzanai J U
- Authors: Nyokong, Tebello , Chidawanyika, Wadzanai J U
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6582 , http://hdl.handle.net/10962/d1004147
- Description: The syntheses of three cadmium phthalocyanine derivatives tetrakis{1,(4)-(4-benzyloxy)phenoxyphthalocyaninato} (5a), tetrakis{1,(4)-(2-pyridyloxy)phthalocyaninato} (5b) and tetrakis{2,(3)-(4-benzyloxy)phenoxyphthalocyaninato} (6a) are reported here for the first time. Spectroscopic and photophysical properties have also been determined and the results are discussed here paying particular attention to the influence of various organic solvents in relation to the position and type of substitution. Singlet oxygen quantum yields (ΦΔ) and photodegradation quantum yields (ΦPd) have also been discussed. The triplet quantum yields have been determined and ranged from ΦT = 0.36 to 0.85, where the peripherally (β) substituted derivatives generally give higher values than those substituted at the non-peripheral (α) positions. The triplet lifetimes ranged from τT = 5 to 40 μs. In all cases (except toluene, due to the lack of data), the highest singlet oxygen quantum yields obtained were for the pyridyloxy-substituted derivatives 5b (ΦΔ = 0.60 in DMF) and 6b (ΦΔ = 0.74 in DMSO).
- Full Text:
- Date Issued: 2009
- Authors: Nyokong, Tebello , Chidawanyika, Wadzanai J U
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6582 , http://hdl.handle.net/10962/d1004147
- Description: The syntheses of three cadmium phthalocyanine derivatives tetrakis{1,(4)-(4-benzyloxy)phenoxyphthalocyaninato} (5a), tetrakis{1,(4)-(2-pyridyloxy)phthalocyaninato} (5b) and tetrakis{2,(3)-(4-benzyloxy)phenoxyphthalocyaninato} (6a) are reported here for the first time. Spectroscopic and photophysical properties have also been determined and the results are discussed here paying particular attention to the influence of various organic solvents in relation to the position and type of substitution. Singlet oxygen quantum yields (ΦΔ) and photodegradation quantum yields (ΦPd) have also been discussed. The triplet quantum yields have been determined and ranged from ΦT = 0.36 to 0.85, where the peripherally (β) substituted derivatives generally give higher values than those substituted at the non-peripheral (α) positions. The triplet lifetimes ranged from τT = 5 to 40 μs. In all cases (except toluene, due to the lack of data), the highest singlet oxygen quantum yields obtained were for the pyridyloxy-substituted derivatives 5b (ΦΔ = 0.60 in DMF) and 6b (ΦΔ = 0.74 in DMSO).
- Full Text:
- Date Issued: 2009
Synthesis and Pd(II) binding studies of octasubstituted alkyl thio derivatised phthalocyanines
- Ogunbayo, T B, Nyokong, Tebello
- Authors: Ogunbayo, T B , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6587 , http://hdl.handle.net/10962/d1004170
- Description: Synthesis and characterization of non-peripherally (4,5) and peripherally (6,7) substituted metal free and Pd octapentylthiophthalocyanine and coordination of palladium ions to these Pcs are reported. The unmetalated complexes (4 and 6) show Pd coordination at the central metal and at the ring. The number of Pd ions bound to complex 4 were found to be five and to complex 6 were three. The equilibrium constant for the binding of Pd to complexes 4 was lower (K = 1.2 × 109 dm3 mol−1) than for complex 6 (K = 5.7 × 1010 dm3 mol−1).
- Full Text:
- Date Issued: 2009
- Authors: Ogunbayo, T B , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6587 , http://hdl.handle.net/10962/d1004170
- Description: Synthesis and characterization of non-peripherally (4,5) and peripherally (6,7) substituted metal free and Pd octapentylthiophthalocyanine and coordination of palladium ions to these Pcs are reported. The unmetalated complexes (4 and 6) show Pd coordination at the central metal and at the ring. The number of Pd ions bound to complex 4 were found to be five and to complex 6 were three. The equilibrium constant for the binding of Pd to complexes 4 was lower (K = 1.2 × 109 dm3 mol−1) than for complex 6 (K = 5.7 × 1010 dm3 mol−1).
- Full Text:
- Date Issued: 2009
Synthesis, spectroscopic and electrochemical properties of manganese, nickel and iron octakis-(2-diethylaminoethanethiol)-phthalocyanine
- Adebayo, A I, Nyokong, Tebello
- Authors: Adebayo, A I , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6563 , http://hdl.handle.net/10962/d1004122
- Description: The syntheses, spectroscopic and electrochemical properties of manganese (3), nickel (4) and iron (5) phthalocyanine complexes, octa-substituted at the peripheral positions with diethlyaminoethanethiol substituent, are reported. The electrochemistry of these complexes and the corresponding cobalt complex (6) are reported. Complex 3 showed two reversible reduction couples attributed to the MnIIIPc−2/MnIIPc−2 (E½ = −0.12 V versus Ag|AgCl) and MnIIPc−2/MnIIPc−3 (E½ = −0.82 V versus Ag|AgCl) species. Two ring-based reduction couples were also observed for complex 4. Two reduction couples, assigned to the FeIIPc−2/FeIPc−2 (E½ = −0.35 V versus Ag|AgCl) and FeIPc−2/FeIPc−3 (E½ = −0.96 V versus Ag|AgCl) species, and an oxidation couple, attributed to FeIIIPc−2/FeIIPc−2 (E½ = 0.26 V versus Ag|AgCl) species, were observed. For complex 6, two reductions and one oxidation were also observed with the potential range of 1.2 to −1.8 V versus Ag|AgCl Spectroelectrochemical studies were used to confirm some of the assigned processes.
- Full Text:
- Date Issued: 2009
- Authors: Adebayo, A I , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6563 , http://hdl.handle.net/10962/d1004122
- Description: The syntheses, spectroscopic and electrochemical properties of manganese (3), nickel (4) and iron (5) phthalocyanine complexes, octa-substituted at the peripheral positions with diethlyaminoethanethiol substituent, are reported. The electrochemistry of these complexes and the corresponding cobalt complex (6) are reported. Complex 3 showed two reversible reduction couples attributed to the MnIIIPc−2/MnIIPc−2 (E½ = −0.12 V versus Ag|AgCl) and MnIIPc−2/MnIIPc−3 (E½ = −0.82 V versus Ag|AgCl) species. Two ring-based reduction couples were also observed for complex 4. Two reduction couples, assigned to the FeIIPc−2/FeIPc−2 (E½ = −0.35 V versus Ag|AgCl) and FeIPc−2/FeIPc−3 (E½ = −0.96 V versus Ag|AgCl) species, and an oxidation couple, attributed to FeIIIPc−2/FeIIPc−2 (E½ = 0.26 V versus Ag|AgCl) species, were observed. For complex 6, two reductions and one oxidation were also observed with the potential range of 1.2 to −1.8 V versus Ag|AgCl Spectroelectrochemical studies were used to confirm some of the assigned processes.
- Full Text:
- Date Issued: 2009
Photophysicochemical and fFluorescence quenching studies of benzyloxyphenoxy substituted zinc phthalocyanines
- Authors: Durmuş, M , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6570 , http://hdl.handle.net/10962/d1004133
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetrakis- and octakis(4-benzyloxyphenoxy)-substituted zinc phthalocyanines (1, 2 and 3). General trends are described for photodegradation, and fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulphoxide (DMSO) and toluene. The fluorescence of the complexes is quenched by benzoquinone (BQ), and fluorescence quenching properties are investigated in DMSO and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2 and 3) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications.
- Full Text:
- Date Issued: 2008
- Authors: Durmuş, M , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6570 , http://hdl.handle.net/10962/d1004133
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetrakis- and octakis(4-benzyloxyphenoxy)-substituted zinc phthalocyanines (1, 2 and 3). General trends are described for photodegradation, and fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulphoxide (DMSO) and toluene. The fluorescence of the complexes is quenched by benzoquinone (BQ), and fluorescence quenching properties are investigated in DMSO and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2 and 3) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications.
- Full Text:
- Date Issued: 2008
The synthesis and electrochemical behaviour of water soluble manganese phthalocyanines: Anion radical versus Mn(I) species
- Sehlotho, Nthapo, Durmuş, M, Ahsen, N, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Durmuş, M , Ahsen, N , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6596 , http://hdl.handle.net/10962/d1004345
- Description: The following MnPc derivatives were synthesized: 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5a), quaternized 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5b), 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (6a) and quaternized 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH)(6b). Spectro-electrochemistry shows that the reduction of Mn(II)Pc to Mn(I)Pc occurs only when the complexes are in their quaternized form (5b and 6b). The reduction (to Mn(I)Pc(−2)) of the quaternized form occurs at a lower potential than that (to Mn(II)Pc(−3)) of the unquaternized form. This observation suggests that metal reduction (to Mn(I)Pc(−2)) versus ligand reduction (to Mn(II)Pc(−3)) in Mn(II)Pc complexes depends on the nature of the ring substituents.
- Full Text:
- Date Issued: 2008
- Authors: Sehlotho, Nthapo , Durmuş, M , Ahsen, N , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6596 , http://hdl.handle.net/10962/d1004345
- Description: The following MnPc derivatives were synthesized: 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5a), quaternized 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5b), 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (6a) and quaternized 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH)(6b). Spectro-electrochemistry shows that the reduction of Mn(II)Pc to Mn(I)Pc occurs only when the complexes are in their quaternized form (5b and 6b). The reduction (to Mn(I)Pc(−2)) of the quaternized form occurs at a lower potential than that (to Mn(II)Pc(−3)) of the unquaternized form. This observation suggests that metal reduction (to Mn(I)Pc(−2)) versus ligand reduction (to Mn(II)Pc(−3)) in Mn(II)Pc complexes depends on the nature of the ring substituents.
- Full Text:
- Date Issued: 2008
Effects of substituents on the photochemical and photophysical properties of main group metal phthalocyanines
- Authors: Nyokong, Tebello
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6581 , http://hdl.handle.net/10962/d1004146
- Description: The review focuses on the photochemical (singlet oxygen and photobleaching quantum yields) and photophysical (triplet quantum yields and lifetimes and fluorescence lifetimes) properties of metallophthalocyanine complexes containing main group metals (Zn, Al, Ge, Si, Sn, Ga and In) and some unmetallated phthalocyanine complexes. Five tables containing photophysical and photochemical data for sulfonated phthalocyanines, tetra-, octa-substituted and unsubstituted phthalocyanines in a variety of solvents, are included in the review.
- Full Text:
- Date Issued: 2007
- Authors: Nyokong, Tebello
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6581 , http://hdl.handle.net/10962/d1004146
- Description: The review focuses on the photochemical (singlet oxygen and photobleaching quantum yields) and photophysical (triplet quantum yields and lifetimes and fluorescence lifetimes) properties of metallophthalocyanine complexes containing main group metals (Zn, Al, Ge, Si, Sn, Ga and In) and some unmetallated phthalocyanine complexes. Five tables containing photophysical and photochemical data for sulfonated phthalocyanines, tetra-, octa-substituted and unsubstituted phthalocyanines in a variety of solvents, are included in the review.
- Full Text:
- Date Issued: 2007
Electrochemical characterisation of tetra- and octa-substituted oxo(phthalocyaninato)titanium(IV) complexes
- Tau, Prudence Lerato, Nyokong, Tebello
- Authors: Tau, Prudence Lerato , Nyokong, Tebello
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6598 , http://hdl.handle.net/10962/d1004347
- Description: The synthesis and electrochemical characterisation of the following oxotitanium tetra-substituted phthalocyanines are reported: 1,(4)-(tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (5a); 1,(4)- {tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (5b); 2,(3)- (tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (6a) and 2,(3)-{tetrakis[4- (benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (6b). The electrochemical characterisation of complexes octa-substituted with 4-(benzyloxy)phenoxy (9b), phenoxy (9c) and tert -butylphenoxy (9d) groups is also reported. The cyclic voltammograms of the complexes exhibit reversible couples I–III and couple IV is quasi-reversible for complexes 5a, 5b, 6a and 6b. The first two reductions are metal-based processes, confirmed by spectroelectrochemistry to be due to Ti IV Pc 2 − /Ti III Pc 2 − and Ti III Pc 2 − /Ti II Pc 2 − redox processes and the last two reductions are ring-based processes due to Ti II Pc 2 − /Ti II Pc 3 − and Ti II Pc 3 − /Ti II Pc 4 − . Chronocoulometry confirmed a one-electron transfer at each reduction step. The electrochemistry of the above complexes is also compared to the previously reported 5c, 5d, 6c and 6d.
- Full Text:
- Date Issued: 2007
- Authors: Tau, Prudence Lerato , Nyokong, Tebello
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6598 , http://hdl.handle.net/10962/d1004347
- Description: The synthesis and electrochemical characterisation of the following oxotitanium tetra-substituted phthalocyanines are reported: 1,(4)-(tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (5a); 1,(4)- {tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (5b); 2,(3)- (tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (6a) and 2,(3)-{tetrakis[4- (benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (6b). The electrochemical characterisation of complexes octa-substituted with 4-(benzyloxy)phenoxy (9b), phenoxy (9c) and tert -butylphenoxy (9d) groups is also reported. The cyclic voltammograms of the complexes exhibit reversible couples I–III and couple IV is quasi-reversible for complexes 5a, 5b, 6a and 6b. The first two reductions are metal-based processes, confirmed by spectroelectrochemistry to be due to Ti IV Pc 2 − /Ti III Pc 2 − and Ti III Pc 2 − /Ti II Pc 2 − redox processes and the last two reductions are ring-based processes due to Ti II Pc 2 − /Ti II Pc 3 − and Ti II Pc 3 − /Ti II Pc 4 − . Chronocoulometry confirmed a one-electron transfer at each reduction step. The electrochemistry of the above complexes is also compared to the previously reported 5c, 5d, 6c and 6d.
- Full Text:
- Date Issued: 2007
Effects of ring substituents on electrocatalytic activity of manganese phthalocyanines towards the reduction of molecular oxygen
- Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6594 , http://hdl.handle.net/10962/d1004343
- Description: Reduction of oxygen electrocatalyzed by adsorbed films of manganese phthalocyanine complexes is reported. The complexes studied were: manganese phthalocyanine (MnPc, 1); manganese tetraamino phthalocyanine (MnTAPc, 2); manganese tetrapentoxy pyrrole phthalocyanine (MnTPePyrPc, 3); manganese tetra phenoxy pyrrole phthalocyanine (MnTPPyrPc, 4); manganese tetra mercaptopyrimidine phthalocyanine (MnTMPyPc, 5) and manganese tetra ethoxy thiophene phthalocyanine (MnTETPc, 6). The reaction was conducted in buffer solutions of pH range 1–12. Rotating disk electrode voltammetry revealed two electron reduction in acidic and slightly alkaline media due to the formation of hydrogen peroxide. In highly basic media, water is the major product formed via four electron transfer. The reaction was found to be first order in the diffusing analyte oxygen.
- Full Text:
- Date Issued: 2006
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6594 , http://hdl.handle.net/10962/d1004343
- Description: Reduction of oxygen electrocatalyzed by adsorbed films of manganese phthalocyanine complexes is reported. The complexes studied were: manganese phthalocyanine (MnPc, 1); manganese tetraamino phthalocyanine (MnTAPc, 2); manganese tetrapentoxy pyrrole phthalocyanine (MnTPePyrPc, 3); manganese tetra phenoxy pyrrole phthalocyanine (MnTPPyrPc, 4); manganese tetra mercaptopyrimidine phthalocyanine (MnTMPyPc, 5) and manganese tetra ethoxy thiophene phthalocyanine (MnTETPc, 6). The reaction was conducted in buffer solutions of pH range 1–12. Rotating disk electrode voltammetry revealed two electron reduction in acidic and slightly alkaline media due to the formation of hydrogen peroxide. In highly basic media, water is the major product formed via four electron transfer. The reaction was found to be first order in the diffusing analyte oxygen.
- 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
Electrocatalysis of oxidation of 2-mercaptoethanol, L-cysteine and reduced glutathione by adsorbed and electrodeposited cobalt tetra phenoxypyrrole and tetra ethoxythiophene substituted phthalocyanines
- Sehlotho, Nthapo, Nyokong, Tebello, Zagal, Jose H, Bedioui, Fethi
- Authors: Sehlotho, Nthapo , Nyokong, Tebello , Zagal, Jose H , Bedioui, Fethi
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6593 , http://hdl.handle.net/10962/d1004342
- Description: Catalytic activity of cobalt tetra ethoxythiophene and cobalt tetra phenoxypyrrole phthalocyanine complexes towards oxidation of 2-mercaptoethanol, L-cysteine and reduced glutathione is reported. It was found that the activity of the complexes depends on the substitution of the phthalocyanine ring, pH, film thickness and method of electrode modification. The high electrocatalytic activity obtained with adsorbed complexes in alkaline medium clearly demonstrates the necessity of modifying bare carbon electrodes to endow them with the desired behaviour.
- Full Text:
- Date Issued: 2006
- Authors: Sehlotho, Nthapo , Nyokong, Tebello , Zagal, Jose H , Bedioui, Fethi
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6593 , http://hdl.handle.net/10962/d1004342
- Description: Catalytic activity of cobalt tetra ethoxythiophene and cobalt tetra phenoxypyrrole phthalocyanine complexes towards oxidation of 2-mercaptoethanol, L-cysteine and reduced glutathione is reported. It was found that the activity of the complexes depends on the substitution of the phthalocyanine ring, pH, film thickness and method of electrode modification. The high electrocatalytic activity obtained with adsorbed complexes in alkaline medium clearly demonstrates the necessity of modifying bare carbon electrodes to endow them with the desired behaviour.
- Full Text:
- Date Issued: 2006