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
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
Electrocatalytic behaviour of carbon paste electrode modified with iron(II) phthalocyanine (FePc) nanoparticles towards the detection of amitrole
- Siswana, Msimelelo P, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Siswana, Msimelelo P , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6591 , http://hdl.handle.net/10962/d1004340
- Description: This paper describes the construction of a carbon paste electrode (CPE) impregnated with nanoparticles of iron(II) phthalocyanine (nanoFePc). The new electrode (nanoFePc-CPE) revealed interesting electrocatalytic behaviour towards amitrole; pure catalytic diffusion-controlled process, with high Tafel slope (235 mV/decade) suggesting strong binding of amitrole with nanoFePc catalyst. The effects of catalyst loading, varying pH and electrolytes were studied. The mechanism for the interaction of amitrole with the nanoFePc is proposed to involve the Fe[superscript (III)]Pc/Fe[superscript (II)]Pc redox process. Using chronoamperometry (E = +0.42 V versus Ag/AgCl) technique, the sensor was reliably employed for amitrole assay at pH 12.0 phosphate buffer (with sodium sulphate as the supporting electrolyte) for up to 12 nM amitrole with excellent sensitivity (ca. 3.44 μA/nM) and low detection limit (3.62 ± 0.11 nM, i.e. 0.305 μg L[superscript (−1)] using the YB + 3σB criterion and 0.85 ± 0.03 nM, i.e. 70 ng/L with the Y[subscript B] + 2[subscript σB] criterion) as well as satisfactory amperometric selectivity coefficient (K[subscript amp] ≈ 7.4 × 10[superscript (−4)] for ammonium thiocyanate, a component of many amitrole herbicides, and 3.2 × 10[superscript (−3)] for asulam pesticide). The surface of the electrode can easily be regenerated by simple polishing on an alumina paper, obtaining a fresh surface ready for use in a new assay. The proposed electrode was successfully applied in the quantification of amitrole in its commercial formulation as well as in tap water samples.
- Full Text:
- Date Issued: 2006
- Authors: Siswana, Msimelelo P , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6591 , http://hdl.handle.net/10962/d1004340
- Description: This paper describes the construction of a carbon paste electrode (CPE) impregnated with nanoparticles of iron(II) phthalocyanine (nanoFePc). The new electrode (nanoFePc-CPE) revealed interesting electrocatalytic behaviour towards amitrole; pure catalytic diffusion-controlled process, with high Tafel slope (235 mV/decade) suggesting strong binding of amitrole with nanoFePc catalyst. The effects of catalyst loading, varying pH and electrolytes were studied. The mechanism for the interaction of amitrole with the nanoFePc is proposed to involve the Fe[superscript (III)]Pc/Fe[superscript (II)]Pc redox process. Using chronoamperometry (E = +0.42 V versus Ag/AgCl) technique, the sensor was reliably employed for amitrole assay at pH 12.0 phosphate buffer (with sodium sulphate as the supporting electrolyte) for up to 12 nM amitrole with excellent sensitivity (ca. 3.44 μA/nM) and low detection limit (3.62 ± 0.11 nM, i.e. 0.305 μg L[superscript (−1)] using the YB + 3σB criterion and 0.85 ± 0.03 nM, i.e. 70 ng/L with the Y[subscript B] + 2[subscript σB] criterion) as well as satisfactory amperometric selectivity coefficient (K[subscript amp] ≈ 7.4 × 10[superscript (−4)] for ammonium thiocyanate, a component of many amitrole herbicides, and 3.2 × 10[superscript (−3)] for asulam pesticide). The surface of the electrode can easily be regenerated by simple polishing on an alumina paper, obtaining a fresh surface ready for use in a new assay. The proposed electrode was successfully applied in the quantification of amitrole in its commercial formulation as well as in tap water samples.
- Full Text:
- Date Issued: 2006
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
Optical nonlinearities and photophysicochemical behaviour of green and blue forms of lutetium bisphthalocyanines
- Sekhosana, Kutloano Edward, Amuhaya, Edith, Mack, John, Nyokong, Tebello
- Authors: Sekhosana, Kutloano Edward , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7316 , http://hdl.handle.net/10962/d1020543
- Description: A rare earth sandwich-type phthalocyanine: bis-{2,3,9,10,16,17,23,24-octa(4-tert-butylphenoxy) phthalocyaninato} lutetium(III) has been synthesized. The photophysical and nonlinear optical behavior of both the “green” and “blue” forms ([LuIIIPc2] and [LuIIIPc2]−, respectively) of the complex have been investigated. High triplet state and singlet oxygen quantum yield values were obtained for the neutral blue form which contains no unpaired electrons. Relatively high third order susceptibility and hyperpolarizability values of the order of 10−10 and 10−28 esu were obtained for both the green and blue forms, respectively. A very low threshold intensity of 0.00051 J cm−2 was obtained for the blue form. Hence the complex shows promise for non-linear optical applications. , Original publication is available at http://dx.doi.org/10.1039/C4TC00505H
- Full Text:
- Authors: Sekhosana, Kutloano Edward , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7316 , http://hdl.handle.net/10962/d1020543
- Description: A rare earth sandwich-type phthalocyanine: bis-{2,3,9,10,16,17,23,24-octa(4-tert-butylphenoxy) phthalocyaninato} lutetium(III) has been synthesized. The photophysical and nonlinear optical behavior of both the “green” and “blue” forms ([LuIIIPc2] and [LuIIIPc2]−, respectively) of the complex have been investigated. High triplet state and singlet oxygen quantum yield values were obtained for the neutral blue form which contains no unpaired electrons. Relatively high third order susceptibility and hyperpolarizability values of the order of 10−10 and 10−28 esu were obtained for both the green and blue forms, respectively. A very low threshold intensity of 0.00051 J cm−2 was obtained for the blue form. Hence the complex shows promise for non-linear optical applications. , Original publication is available at http://dx.doi.org/10.1039/C4TC00505H
- Full Text:
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
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 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
Optical nonlinearities in non-peripherally substituted pyridyloxy phthalocyanines: a combined effect of symmetry, ring-strain and demetallation
- Sanusi, Kayode, Antunes, Edith M, Nyokong, Tebello
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7301 , http://hdl.handle.net/10962/d1020375
- Description: The optical nonlinearities of six non-peripherally-substituted pyridyloxy phthalocyanines have been studied at 532 nm using a nanosecond Z-scan technique in a dimethyl sulphoxide solution. Ring-strain effects and the absence of a metal center were found to greatly reduce the inherent high nonlinearities expected of some of these phthalocyanine complexes. Of the six molecules investigated, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyaninato lead(II) 3, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyanine 5, and 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyanine 6 were found to exhibit negligible nonlinear optical behavior, due to either the absence of asymmetry or central metal and/or the presence of a ring-strain effect. A two-photon absorption process was found to be the major contributor to the observed reverse saturable absorption (RSA) in 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyaninato lead(II) 4, 1(4)-mono-(2-pyridyloxy)phthalocyaninato lead(II) 7, and 1(4)-mono-(4-pyridyloxy)phthalocyaninato lead(II) 8, with large two-photon absorption cross-section, high hyperpolarizability and high third-order susceptibility values in the range of 4.53 × 10−43–5.33 × 10−42 cm4 s per photon, 1.61 × 10−28–1.89 × 10−27 esu and 9.73 × 10−12–7.05 × 10−11 esu respectively. , Original publication is available at http://dx.doi.org/10.1039/C3DT52462K , Arbortext Advanced Print Publisher 9.1.520/W Unicode , Acrobat Distiller 10.0.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
- Full Text:
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7301 , http://hdl.handle.net/10962/d1020375
- Description: The optical nonlinearities of six non-peripherally-substituted pyridyloxy phthalocyanines have been studied at 532 nm using a nanosecond Z-scan technique in a dimethyl sulphoxide solution. Ring-strain effects and the absence of a metal center were found to greatly reduce the inherent high nonlinearities expected of some of these phthalocyanine complexes. Of the six molecules investigated, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyaninato lead(II) 3, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyanine 5, and 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyanine 6 were found to exhibit negligible nonlinear optical behavior, due to either the absence of asymmetry or central metal and/or the presence of a ring-strain effect. A two-photon absorption process was found to be the major contributor to the observed reverse saturable absorption (RSA) in 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyaninato lead(II) 4, 1(4)-mono-(2-pyridyloxy)phthalocyaninato lead(II) 7, and 1(4)-mono-(4-pyridyloxy)phthalocyaninato lead(II) 8, with large two-photon absorption cross-section, high hyperpolarizability and high third-order susceptibility values in the range of 4.53 × 10−43–5.33 × 10−42 cm4 s per photon, 1.61 × 10−28–1.89 × 10−27 esu and 9.73 × 10−12–7.05 × 10−11 esu respectively. , Original publication is available at http://dx.doi.org/10.1039/C3DT52462K , Arbortext Advanced Print Publisher 9.1.520/W Unicode , Acrobat Distiller 10.0.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
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Novel amperometric glucose biosensor based on an ether-linked cobalt(II) phthalocyaninecobalt(II) tetraphenylporphyrin pentamer as a redox mediator
- Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6583 , http://hdl.handle.net/10962/d1004148
- Description: The development of cobalt(II) phthalocyanine–cobalt(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin), (CoPc–(CoTPP)[subscript 4]) pentamer as a novel redox mediator for amperometric enzyme electrode sensitive to glucose is described. A glassy carbon electrode (GCE) was first modified with the pentamer, then followed by the immobilization onto the GCE–CoPc–(CoTPP)[subscript 4] with glucose oxidase (GOx) through cross-linking with glutaraldehyde in the presence of bovine serum albumin (BSA) and Nafion® cation-exchange polymer. The proposed biosensor displayed good amperometric respose charateristics to glucose in pH 7.0 PBS solution; such as low overpotentials (+400 mV versus Ag|AgCl), very fast amperometric response time (~5 s), linear concentration range extended up to 11 mM, with 10 μM detection limit. The biosensor exhibited electrochemical Michaelis–Menten kinetics and showed an average apparent Michaelis–Menten constant (K′M) of 14.91 ± 0.46 mM over a storage period of 2 weeks.
- Full Text:
- Date Issued: 2006
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6583 , http://hdl.handle.net/10962/d1004148
- Description: The development of cobalt(II) phthalocyanine–cobalt(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin), (CoPc–(CoTPP)[subscript 4]) pentamer as a novel redox mediator for amperometric enzyme electrode sensitive to glucose is described. A glassy carbon electrode (GCE) was first modified with the pentamer, then followed by the immobilization onto the GCE–CoPc–(CoTPP)[subscript 4] with glucose oxidase (GOx) through cross-linking with glutaraldehyde in the presence of bovine serum albumin (BSA) and Nafion® cation-exchange polymer. The proposed biosensor displayed good amperometric respose charateristics to glucose in pH 7.0 PBS solution; such as low overpotentials (+400 mV versus Ag|AgCl), very fast amperometric response time (~5 s), linear concentration range extended up to 11 mM, with 10 μM detection limit. The biosensor exhibited electrochemical Michaelis–Menten kinetics and showed an average apparent Michaelis–Menten constant (K′M) of 14.91 ± 0.46 mM over a storage period of 2 weeks.
- Full Text:
- Date Issued: 2006
Preferential electrosorption of cobalt (II) tetra-aminophthalocyanine at single-wall carbon nanotubes immobilized on a basal plane pyrolytic graphite electrode
- Ozoemena, Kenneth I, Pillay, J, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Pillay, J , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6584 , http://hdl.handle.net/10962/d1004160
- Description: This communication describes the preferential electrosorption of cobalt (II) tetra-aminophthalocyanine (CoTAPc) (rather than the expected electropolymerisation) onto a SWCNT immobilized on a basal plane pyrolytic graphite electrode (BPPGE). Cyclic voltammetric and electrochemical impedance spectroscopic data revealed that the electrosorbed CoTAPc is highly stable, well organized with comparable electron-transfer rate constant in ferricyanide solution (k[subscript app] ~ 6 × 10[superscript (−5)] cm s[superscript (−1)] order) to that of the SWNCT. Electrochemical kinetics of the electrosorbed CoTAPc yielded k[subscript s] of 0.169 s[superscript (−1)] and 832.2 s[superscript (−1)] for the cathodic and anodic reactions, respectively, indicative of different rate-determining steps for the cathodic and anodic reactions. Strong π-stacking interactions between CoTAPc and the sidewalls of the SWCNTs, with possible synergistic covalent interactions, are explained as responsible for the preferential electrosorption process. Both BPPGE-SWCNT-CoTAPc[subscript (ads)] and BPPGE-SWCNT showed comparable electrocatalytic responses towards the detection of 2-(diethylamino) ethanethiol (DEAET).
- Full Text:
- Date Issued: 2006
- Authors: Ozoemena, Kenneth I , Pillay, J , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6584 , http://hdl.handle.net/10962/d1004160
- Description: This communication describes the preferential electrosorption of cobalt (II) tetra-aminophthalocyanine (CoTAPc) (rather than the expected electropolymerisation) onto a SWCNT immobilized on a basal plane pyrolytic graphite electrode (BPPGE). Cyclic voltammetric and electrochemical impedance spectroscopic data revealed that the electrosorbed CoTAPc is highly stable, well organized with comparable electron-transfer rate constant in ferricyanide solution (k[subscript app] ~ 6 × 10[superscript (−5)] cm s[superscript (−1)] order) to that of the SWNCT. Electrochemical kinetics of the electrosorbed CoTAPc yielded k[subscript s] of 0.169 s[superscript (−1)] and 832.2 s[superscript (−1)] for the cathodic and anodic reactions, respectively, indicative of different rate-determining steps for the cathodic and anodic reactions. Strong π-stacking interactions between CoTAPc and the sidewalls of the SWCNTs, with possible synergistic covalent interactions, are explained as responsible for the preferential electrosorption process. Both BPPGE-SWCNT-CoTAPc[subscript (ads)] and BPPGE-SWCNT showed comparable electrocatalytic responses towards the detection of 2-(diethylamino) ethanethiol (DEAET).
- Full Text:
- Date Issued: 2006
Solvent effects on the photochemical and fluorescence properties of zinc phthalocyanine derivatives
- Ogunsipe, Abimbola Olukayode, Maree, D, Nyokong, Tebello
- Authors: Ogunsipe, Abimbola Olukayode , Maree, D , Nyokong, Tebello
- Date: 2003
- Language: English
- Type: Article
- Identifier: vital:6586 , http://hdl.handle.net/10962/d1004162 , http://dx.doi.org/10.1016/S0022-2860(03)00155-8
- Description: The effects of solvents on the singlet oxygen, photobleaching and fluorescence quantum yields for zinc phthalocyanine (ZnPc) and its derivatives; (pyridino)zinc phthalocyanine ((py)ZnPc), zinc octaphenoxyphthalocyanine (ZnOPPc) and zinc octaestronephthalocyanine (ZnOEPc), is presented. The effects of the solvents on the ground state spectra are also discussed. The largest red shift of the Q band was observed in aromatic solvents, the highest shift being observed for 1-chloronaphthalene. Higher singlet fluorescence quantum yields were observed in THF for ZnPc and ZnOPPC. Also in the same solvent phototransformation rather than photobleaching was observed for ZnOPPc. Split Q band in the emission and excitation spectra of ZnOPPc was observed in some solvents and this is explained in terms of the lowering of symmetry following excitation.
- Full Text:
- Date Issued: 2003
- Authors: Ogunsipe, Abimbola Olukayode , Maree, D , Nyokong, Tebello
- Date: 2003
- Language: English
- Type: Article
- Identifier: vital:6586 , http://hdl.handle.net/10962/d1004162 , http://dx.doi.org/10.1016/S0022-2860(03)00155-8
- Description: The effects of solvents on the singlet oxygen, photobleaching and fluorescence quantum yields for zinc phthalocyanine (ZnPc) and its derivatives; (pyridino)zinc phthalocyanine ((py)ZnPc), zinc octaphenoxyphthalocyanine (ZnOPPc) and zinc octaestronephthalocyanine (ZnOEPc), is presented. The effects of the solvents on the ground state spectra are also discussed. The largest red shift of the Q band was observed in aromatic solvents, the highest shift being observed for 1-chloronaphthalene. Higher singlet fluorescence quantum yields were observed in THF for ZnPc and ZnOPPC. Also in the same solvent phototransformation rather than photobleaching was observed for ZnOPPc. Split Q band in the emission and excitation spectra of ZnOPPc was observed in some solvents and this is explained in terms of the lowering of symmetry following excitation.
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- Date Issued: 2003
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.
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- 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.
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- Date Issued: 2004
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).
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- Date Issued: 2009
Physicochemical properties of a zinc phthalocyanine – pyrene conjugate adsorbed onto single walled carbon nanotubes
- Ogbodu, Racheal O, Antunes, Edith M, Nyokong, Tebello
- Authors: Ogbodu, Racheal O , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7328 , http://hdl.handle.net/10962/d1020589
- Description: A conjugate between zinc monoamino phthalocyanine (ZnMAPc) and pyrene (Py) represented as ZnMAPc–Py (complex 3) was synthesized and characterized by various spectroscopic techniques and by elemental analysis. This manuscript also reports on the photochemical and photophysical properties of 3. This new compound exhibited higher triplet, fluorescence and singlet oxygen quantum yields in comparison to the phthalocyanine alone, hence showing the advantages of attaching pyrene to the Pc without breaking the conjugation. We also observed a decrease in photophysical parameters upon adsorbing the ZnMAPc–Py complex onto single walled carbon nanotubes (SWCNT). However, ZnMAPc–Py still generated some singlet oxygen when adsorbed onto SWCNT. , Original publication is available at http://dx.doi.org/10.1039/C3DT50335F
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- Authors: Ogbodu, Racheal O , Antunes, Edith M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7328 , http://hdl.handle.net/10962/d1020589
- Description: A conjugate between zinc monoamino phthalocyanine (ZnMAPc) and pyrene (Py) represented as ZnMAPc–Py (complex 3) was synthesized and characterized by various spectroscopic techniques and by elemental analysis. This manuscript also reports on the photochemical and photophysical properties of 3. This new compound exhibited higher triplet, fluorescence and singlet oxygen quantum yields in comparison to the phthalocyanine alone, hence showing the advantages of attaching pyrene to the Pc without breaking the conjugation. We also observed a decrease in photophysical parameters upon adsorbing the ZnMAPc–Py complex onto single walled carbon nanotubes (SWCNT). However, ZnMAPc–Py still generated some singlet oxygen when adsorbed onto SWCNT. , Original publication is available at http://dx.doi.org/10.1039/C3DT50335F
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Chemistry Department: we are chemicals all over
- Authors: Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7173 , http://hdl.handle.net/10962/d1006080
- Description: National University of Lesotho publication: The Light in the Night article by Tebello Nyokong on the Chemistry Department
- Full Text:
- Authors: Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7173 , http://hdl.handle.net/10962/d1006080
- Description: National University of Lesotho publication: The Light in the Night article by Tebello Nyokong on the Chemistry Department
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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.
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- Date Issued: 2007
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.
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- Date Issued: 2013
Synthesis and electrochemical characterisation of benzylmercapto and dodecylmercapto tetra substituted cobalt, iron, and zinc phthalocyanines complexes
- Nyokong, Tebello, Ozoemena, Kenneth I, Agboola, Bolade O
- Authors: Nyokong, Tebello , Ozoemena, Kenneth I , Agboola, Bolade O
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6580 , http://hdl.handle.net/10962/d1004143
- Description: The work reports on cyclic voltammetry (CV), square wave voltammetry and spectroelectrochemistry of the following complexes: tetrakis (benzyl mercapto) phthalocyanine complexes of Zn(II) (ZnTBMPc, 4a ), Co(II) (CoTBMPc, 5a ), Fe(II) (FeTBMPc 6a ); and tetrakis (dodecylmercapto) phthalocyanine complexes of Zn(II) (ZnTDMPc, 4b), Co(II) (CoTDMPc, 5b) and Fe(II) (FeTDMPc, 6b). More reversible CV couples were observed for complexes 4a, 5a and 6a containing thiol phenyl ring substituents. Complexes 4b, 5b and 6b containing long chain thiol substituents showed less reversible couples. Complexes 6a and 6b showed a relatively large number of redox processes (5 for 6a and 6 for 6b) within the potential window employed in this work. The processes for FePc derivatives (6a) are assigned to FeIIIPc-1/FeIIIPc-2, FeIIIPc-2/FeIIPc-2, FeIIPc-2/FeIPc-2, FeIPc-2/FeIPc-3 and FeIPc-3/FeIPc-4 and for the CoPc derivative (5a) to CoIIIPc-1/CoIIIPc-2, CoIIIPc-2/CoIIPc-2, CoIIPc-2/CoIPc-2 and CoIPc-2/CoIPc-3.
- Full Text:
- Date Issued: 2006
- Authors: Nyokong, Tebello , Ozoemena, Kenneth I , Agboola, Bolade O
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6580 , http://hdl.handle.net/10962/d1004143
- Description: The work reports on cyclic voltammetry (CV), square wave voltammetry and spectroelectrochemistry of the following complexes: tetrakis (benzyl mercapto) phthalocyanine complexes of Zn(II) (ZnTBMPc, 4a ), Co(II) (CoTBMPc, 5a ), Fe(II) (FeTBMPc 6a ); and tetrakis (dodecylmercapto) phthalocyanine complexes of Zn(II) (ZnTDMPc, 4b), Co(II) (CoTDMPc, 5b) and Fe(II) (FeTDMPc, 6b). More reversible CV couples were observed for complexes 4a, 5a and 6a containing thiol phenyl ring substituents. Complexes 4b, 5b and 6b containing long chain thiol substituents showed less reversible couples. Complexes 6a and 6b showed a relatively large number of redox processes (5 for 6a and 6 for 6b) within the potential window employed in this work. The processes for FePc derivatives (6a) are assigned to FeIIIPc-1/FeIIIPc-2, FeIIIPc-2/FeIIPc-2, FeIIPc-2/FeIPc-2, FeIPc-2/FeIPc-3 and FeIPc-3/FeIPc-4 and for the CoPc derivative (5a) to CoIIIPc-1/CoIIIPc-2, CoIIIPc-2/CoIIPc-2, CoIIPc-2/CoIPc-2 and CoIPc-2/CoIPc-3.
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- Date Issued: 2006
Tebello Nyokong’s Letter to her 18-year-old Self
- Authors: Nyokong, Tebello
- Type: text , Article
- Identifier: vital:7210 , http://hdl.handle.net/10962/d1006420
- Description: Dr. Nyokong’s is the director of the Nanotechnology Innovation Center at Rhodes University, South Africa and the first South African scientist to win the L’Oréal-UNESCO award for women in science. Her research focus on the development of molecules similar to the ones used to dye blue jeans, which can be used as chemical sensors to detect disease-related molecules and organisms, as an alternative to chemotherapy for the treatment of cancer and for environmental clean-up. [Don't miss the video at the end where she talks about her path and research].
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- Authors: Nyokong, Tebello
- Type: text , Article
- Identifier: vital:7210 , http://hdl.handle.net/10962/d1006420
- Description: Dr. Nyokong’s is the director of the Nanotechnology Innovation Center at Rhodes University, South Africa and the first South African scientist to win the L’Oréal-UNESCO award for women in science. Her research focus on the development of molecules similar to the ones used to dye blue jeans, which can be used as chemical sensors to detect disease-related molecules and organisms, as an alternative to chemotherapy for the treatment of cancer and for environmental clean-up. [Don't miss the video at the end where she talks about her path and research].
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