Catalytic activity of iron and cobalt phthalocyanine complexes towards the oxidation of cyclohexene using tert-butylhydroperoxide and chloroperoxybenzoic acid
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290257 , vital:56729 , xlink:href="https://doi.org/10.1016/j.molcata.2003.08.014"
- Description: Cyclohexene oxidation using tert-butylhydroperoxide (TBHP) or chloroperoxybenzoic acid (CPBA) in the presence of iron(II) polychlorophthalocyanine (Cl16PcFe), iron(II) phthalocyanine (PcFe) and cobalt(II) phthalocyanine (PcCo), results in the formation of the following products: cyclohexene oxide, 2-cyclohexene-1-ol and 2-cyclohexene-1-one. Adipic acid was also formed after long reaction times. The selectivity for 2-cyclohexene-1-one is favoured when Cl16PcFe or PcCo catalysts are employed, while PcFe is selective towards the formation of 2-cyclohexene-1-ol. The Cl16PcFe catalyst is transformed into a μ-oxo dimer (Cl16PcFeIIIOIIIFePcCl16) during the oxidation process. The catalytic process using the unsubstituted PcCoII and PcFeII catalysts involved PcMIII species as an intermediate. The active form of the Cl16PcFe catalyst was stable to degradation in that it was still active even after 4 weeks of continued catalysis.
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- Date Issued: 2004
Cobalt Phthalocyanine Molecular Electrode for the Electrochemical Investigation of the Release of Glutathione upon Copper-Catalyzed Decomposition of S-Nitrosoglutathione
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281201 , vital:55701 , xlink:href="https://doi.org/10.1002/elan.200603656"
- Description: Decomposition of S-nitrosoglutathione (GSNO) in phosphate buffer solution at physiological pH 7.4 in the presence of cuprous ion as a catalyst and sodium borohydride as a reducing agent is analyzed by observing the transient apparition of reduced glutathione GSH through its electrooxidation. Transient formation of GSH, upon decomposition of 1 mM GSNO in presence of 0.025 mM Cu(NO3)2 and 1 mM NaBH4 was detected by using an ordinary pyrolytic graphite electrode modified with an adsorbed monolayer of cobalt phthalocyanine at 0 V vs. SCE.
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- Date Issued: 2007
Effects of ring substituents on electrocatalytic activity of manganese phthalocyanines towards the reduction of molecular oxygen
- 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.
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- Date Issued: 2006
Effects of the number of ring substituents of cobalt carboxyphthalocyanines on the electrocatalytic detection of nitrite, cysteine and melatonin
- Authors: Matemadombo, Fungisai , Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263408 , vital:53625 , xlink:href="https://doi.org/10.1142/S108842460900125X"
- Description: Cobalt phthalocyanine (CoPc), cobalt tetracarboxy phthalocyanine (CoTCPc) and cobalt octacarboxy phthalocyanine (CoOCPc), adsorbed onto glassy carbon electrodes, have been used for the electrocatalytic detection of nitrite, L-cysteine and melatonin. The modified electrodes electrocatalytically detected nitrite around 800 mV vs.Ag|AgCl, a value less positive compared to that of an unmodified glassy carbon electrode (at 950 mV vs.Ag|AgCl) and also gave detection limits in the 10-7 M range for nitrite detection. L-cysteine was detected by the modified electrodes at potentials between 0.50 to 0.65 V vs.Ag|AgCl, with L-cysteine detection limits also in the 10-7 M range. The detection limits for melatonin ranged from 10-7 to 10-6 M. CoPc-modified electrodes displayed good separation of interferents (tryptophan and ascorbic acid) in the presence of melatonin. Analyses of commercial melatonin tablets using modified electrodes gave excellent agreement with manufacturer's value for all modified electrodes of this work.
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- Date Issued: 2009
Electro-catalyzed oxidation of reduced glutathione and 2-mercaptoethanol by cobalt phthalocyanine-containing screen printed graphite electrodes
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Ruillé, Nadine , Boujtita, Mohammed , Nyokong, Tebello , Bedioui, Fethi
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265935 , vital:53902 , xlink:href="https://doi.org/10.1016/j.msec.2007.10.054"
- Description: Electro-catalytic behavior of screen printed graphite electrodes modified with cobalt phthalocyanine (CoPc) towards the oxidation of reduced glutathione (GSH) and 2-mercaptoethanol (2-ME) is reported. We find, by using cyclic voltammetry, that the oxidation of 2-ME occurs at 0.2 V vs Ag/AgCl and − 0.3 vs Ag/AgCl V at pH = 7 and pH = 13, respectively and that of GSH occurs at 0.4 V vs Ag/AgCl and 0.0 V vs Ag/AgCl at pH = 7 and 13, respectively. The electro-catalytic activity depends on the method of electrode modification and the amount of catalyst incorporated in the ink used to fabricate the SPCEs. The highest activity was obtained with electrodes prepared with 2.5% (w:w) of CoPc.
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- Date Issued: 2008
Electrocatalysis of oxidation of 2-mercaptoethanol, L-cysteine and reduced glutathione by adsorbed and electrodeposited cobalt tetra phenoxypyrrole and tetra ethoxythiophene substituted phthalocyanines
- 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.
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- Date Issued: 2006
Electrocatalytic oxidation of thiocyanate, L-cysteine and 2-mercaptoethanol by self-assembled monolayer of cobalt tetraethoxy thiophene phthalocyanine
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283814 , vital:55993 , xlink:href="https://doi.org/10.1016/j.electacta.2005.12.024"
- Description: Catalytic activity of a self-assembled monolayer (SAM) of cobalt tetra ethoxythiophene phthalocyanine (CoTEThPc-SAM) complex towards oxidation of thiocyanate (SCN−), L-cysteine (CYS) and 2-mercaptoethanol (2-ME) is reported. The oxidation of thiocyanate occurs via a two electron transfer, whereas L-cysteine and 2-ME require 1 electron. The oxidation of thiocyanate is catalysed by ring based processes, while L-cysteine is catalysed by both CoIII/CoII process and by ring based processes. 2-ME is catalysed by CoIII/CoII process. The oxidation of thiocyanate on CoTEThPc was performed in acid media instead of basic media commonly employed. The reaction order was found to be unity for all the analytes, showing that only one molecule of analyte interacts with one molecule of the catalyst during the rate determining step.
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- Date Issued: 2006
Electrochemical and electrocatalytic properties of α-substituted manganese and titanium phthalocyanines
- Authors: Nombona, Nolwazi , Tau, Prudence , Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268587 , vital:54212 , xlink:href="https://doi.org/10.1016/j.electacta.2007.11.046"
- Description: This work reports on the synthesis of manganese and titanium phthalocyanine complexes that are tetra-substituted at four non-peripheral positions with amino ligands. The complexes are investigated for the first time for their electrochemical properties using cyclic voltammetry, rotating disc electrode voltammetry and spectroelectrochemistry. Electropolymerisation on a glassy carbon electrode was performed with ease and the modified electrodes were investigated for electrocatalysis of nitrite oxidation. Nitrite oxidation to nitrate is confirmed from the transfer of a total of two electrons.
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- Date Issued: 2008
Phthalocyanines : photochemical, electrochemical and biomimetic catalytic behaviour
- Authors: Sehlotho, Nthapo
- Date: 2007
- Subjects: Phthalocyanines Photochemistry Electrochemistry Biomimetics Oxidation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4336 , http://hdl.handle.net/10962/d1004997
- Description: This thesis explored use of metallophthalocyanines as electrocatalysts towards thiol and thiocyanate oxidation, nitrosothiol decomposition and reduction of oxygen, as well as biomimetic and photo-catalysts of cyclohexene oxidation. 2-mercaptoethanol (2-ME), L-cysteine (CYS) and reduced glutathione (GSH) thiols were oxidized on cobalt tetra ethoxythiophene and cobalt tetra phenoxy pyrrole phthalocyanine modified glassy carbon electrodes, whose catalytic activity was found to depend on pH, film thickness and method of electrode modification. Oxidation of thiocyanate (SCN-), CYS and 2-ME was catalyzed by a selfassembled monolayer of cobalt tetraethoxythiophene Thiocyanate oxidation occurred via two electron transfer, whereas that of CYS and 2-ME required 1 electron. The oxidations of SCN- and 2-ME were catalyzed by ring based processes, while CYS was catalyzed by both Co[superscript III]/Co[superscript II] process and ring-based processes. Oxidation of GSH and 2-ME was conducted on screen printed graphite electrodes modified with cobalt phthalocyanine. Activity depended on method of electrode modification and CoPc % composition. Decomposition of Snitrosoglutathione occurred in the presence of copper ions and NaBH[subscript 4]. Reduced and oxidized glutathione were detected as products using cobalt phthalocyanine adsorbed on an ordinary pyrolytic graphite electrode. Reduction of oxygen was electro-catalyzed by adsorbed manganese phthalocyanine complexes on glassy carbon electrodes. FePc, FePc(Cl)[subscript 16], CoPc and CoPc substituted with phenoxypyrrole and ethoxythiophene ligands were also used as electro-catalysts. Oxygen reduction occurred via two electron transfer in acidic and neutral media forming hydrogen peroxide, while water was formed in basic media via four electron transfer. Cyclohexene oxidation using tert-butylhydroperoxide or chloroperoxy benzoic acid as oxidants in the presence of FePc, FePc(Cl)[subscript 16] and CoPc formed cyclohexene oxide, 2-cyclohexen-1-ol, 2- cyclohexen-1-one and adipic acid. Product selectivity depended on the nature of catalyst and oxidant. The FePc(Cl)[subscript 16] catalyst was transformed into a µ-oxo dimer during the oxidation process while M[superscript III]Pc intermediates were formed with Co[superscript II]Pc and Fe[superscript II]Pc catalysts. Cyclohexene photooxidation catalyzed by zinc phthalocyanine using either red or white light formed 2-cyclohexen-1-one, 2-cyclohexen-1-ol, transcyclohexane diol, cyclohexene oxide and cyclohexene hydroperoxide via singlet oxygen and radical mechanisms. Product yields depended on the light wavelength and intensity, solvent, irradiation time and the rate of photodegradation of the catalyst.
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- Date Issued: 2007
The synthesis and electrochemical behaviour of water soluble manganese phthalocyanines: Anion radical versus Mn(I) species
- Authors: Sehlotho, Nthapo , Durmuş, Mahmut , 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.
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- Date Issued: 2008
Zinc phthalocyanine photocatalyzed oxidation of cyclohexene
- Authors: Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289399 , vital:56629 , xlink:href="https://doi.org/10.1016/j.molcata.2004.05.010"
- Description: Cyclohexene photooxidation catalyzed by zinc phthalocyanine (ZnPc) using either red or white light results in the formation of cyclohexenone, cyclohexenol, trans-cyclohexanediol, cyclohexene oxide and cyclohexene hydroperoxide. The product yield increased as follows: cyclohexenone > cyclohexenol > trans-cyclohexanediol > cyclohexene oxide > cyclohexene hydroperoxide. The mechanism for the formation of these products involves both singlet oxygen and radicals (Type II and Type I mechanisms, respectively). The catalyst degraded slowly when low light intensities were employed. The product yields were found to depend on the light intensity, the nature of solvent, irradiation time and the rate of photodegradation of the catalyst.
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- Date Issued: 2004