Electrocatalytic oxidation of cysteine by molybdenum (V) phthalocyanine complexes
- Authors: Mafatle, Tsukutlane J , Nyokong, Tebello
- Date: 1996
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293369 , vital:57079 , xlink:href="https://doi.org/10.1016/0022-0728(95)04519-8"
- Description: Chemically modified electrodes, constructed by incorporating oxomolybdenum(V) phthalocyanine (OMo(V)(OH)Pc, Pc = phthalocyanine dianion) into graphite powder were used to catalyse the oxidation of cysteine. Solution catalysis of cysteine by oxomolybdenum(V) tetrasulfophthalocyanine, [OMo(V)(OH)TSPc]4−, was also investigated. A considerable reduction in overpotential for cysteine oxidation was observed. Cysteine oxidation occurred at 0.26 and 0.28 V vs. Ag/vbAgCl for catalysis by Omo(V)(OH)Pc and [OMo(V)(OH)TSPc]4− respectively as opposed to 0.77 V vs. Ag/vbAgCl observed on CoPc chemically modified electrodes. The anodic peak currents vary linearly with cysteine concentration in the range 0.02 to 0.08 mol dm−3 and 0.008 to 0.02 mol dm−3 for [OMo(V)(OH)TSPc]4− and OMo(V)Pc respectively.
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- Date Issued: 1996
Pharmacokinetics of cyclizine following intravenous administration to human volunteers
- Authors: Kanfer, Isadore , Walker, Roderick B
- Date: 1996
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184389 , vital:44214 , xlink:href="https://doi.org/10.1016/0928-0987(96)00177-7"
- Description: The pharmacokinetics of cyclizine, a piperazine derivative useful in the prevention and treatment of nausea and vomiting, was investigated in six healthy male volunteers following an intravenous bolus dose. The drug is extensively distributed with a mean volume of distribution of 16.50 ± 3.33 l/kg and a mean total clearance of 0.870 ± 0.105 l/h per kg. Urinary excretion data showed that less than one percent of the dose was excreted up to 36 h as unchanged drug in the urine. The extremely low mean renal clearance (0.005 ± 0.002 l/h per kg) for the parent drug comprised only a small proportion of total clearance indicating that urinary excretion of parent drug is not a major route of elimination for cyclizine. The drug appears to exhibit biexponential pharmacokinetics and has a terminal elimination half-life of approximately 13 h.
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- Date Issued: 1996
Photochemically induced electron transfer between sulfur dioxide and tin (IV) mono-and di-phthalocyanines
- Authors: Nensala, Ngudiankama , Nzimande, Ayanda , Nyokong, Tebello
- Date: 1996
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293402 , vital:57082 , xlink:href="https://doi.org/10.1016/1010-6030(96)04344-4"
- Description: Photolysis, using radiation from a tungsten lamp, of tin diphthalocyanine (Pc2Sn(IV)) in dichloromethane containing SO2 results in the one-electron oxidation of this species to [Pc(−2)Sn(IV)Pc(−1)]+. The relative quantum yields for the formation of the oxidized species were in the order of 10−3. The one-electron oxidized complex was also formed when Pc2Sn was photolysed in an acetonitrile/dichloromethane solvent mixture. Photolysis of the monomeric (L)2Sn(IV)Pc(LOH−, Cl−, Br− and F−) in pyridine and in the presence of SO2 resulted in the reduction of these species to (L)2Sn(IV)Pc(−3)]− with quantum yields in the order of 10−2.
- Full Text:
- Date Issued: 1996
Spectroelectrochemical studies of tin (IV) diphthalocyanine
- Authors: Nensala, Ngudiankama , Nyokong, Tebello
- Date: 1996
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293436 , vital:57085 , xlink:href="https://doi.org/10.1016/0277-5387(95)00325-1"
- Description: Cyclic voltammetry of tin(IV) diphthalocyanine (Pc2Sn) in dichloromethane containing TEAP shows two reduction couples at −0.56 and −0.89 versus saturated calomel electrode (SCE) and one oxidation couple at 0.35 V versus SCE; all were quasireversible one-electron couples. The oxidation couple corresponds to [Pc(−1)SnIVPc(−2)+/Pc(−2)SnIVPc(−2) and the reduction couples to Pc(−2)SnIVPc(−2)/[Pc(−3)SnIVPc(−2)]− and [Pc(−3)SnIVPc(−2)]−/[Pc(−3)SnIVPc(−3)]2−, respectively. The electronic absorption spectra of the various reduced or oxidized tin(IV) diphthalocyanine species are reported.
- Full Text:
- Date Issued: 1996
Equilibrium and kinetic studies of the reaction between pyridine and cobalt (II) phthalocyanine in DMSO
- Authors: Nyokong, Tebello
- Date: 1995
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293380 , vital:57080 , xlink:href="https://doi.org/10.1016/0277-5387(95)00090-F"
- Description: Kinetics and equilibria for the reaction between pyridine and cobalt(II) phthalocyanine [CoPc] (H2Pc = phthalocyanine) in dimethyl sulphoxide (DMSO) were studied at 25°C. The complex, CoPc(py)2, is formed in two consecutive steps. The formation of the mono-substituted CoPc(py)(DMSO) occurs first with a pseudo-first-order rate constant of k1f = 7.7 ± 0.3 × 10−3 dm3 mol−1 s−1. The final disubstituted CoPc(py)2 complex is formed with k2f= 1.1 ± 0.1 × 10−4dm3mol−1−1. The equilibrium constants were found to be K1 = 160 ± 20dm3 mol−1 and K2 = 15 ± 3 dm3mol−1 for the formation of CoPc(py)(DMSO) and CoPc(py)2, respectively.
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- Date Issued: 1995
The reaction of cyanide with iron (II) hexadecachlorophthalocyanine
- Authors: Nyokong, Tebello
- Date: 1995
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293447 , vital:57086 , xlink:href="https://doi.org/10.1016/0277-5387(94)00291-L"
- Description: Kinetics and equilibria for the reaction between cyanide and iron(II) hexadecachlorophthalocyanine ((Cl)16PcFe(DMSO)2, where Pc(−2) = phthalocyanine dianion) in dimethyl sulphoxide (DMSO) are reported. Only the spectrophotometric changes due to the formation of the dicyano, [(Cl)16PcFe(CN)2]2−, complex were observed. This complex is formed with the equilibrium constant, K3 = 1.6 × 103 dm3 mol−1 and a rate constant of k3f = 4.2 × 10−3 dm3 mol−1 s−1. The K2[(Cl)16PcFe(CN)2] complex dissolves in DMSO and dimethyl formamide (DMF) with ϵ = 110 000 and 92 000 dm3 mol−1 cm−1, respectively.
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- Date Issued: 1995
Cyclic voltammetry and photooxidation of molybdenum (V) phthalocyanine
- Authors: Nyokong, Tebello
- Date: 1994
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/295475 , vital:57344 , xlink:href="https://doi.org/10.1016/S0277-5387(00)86594-8"
- Description: Cyclic voltammetry of OMoV(OH)Pc in chloronaphthalene shows two quasi-reversible oxidation couples at 0.38 and 1.22 V and three quasi-reversible reduction couples at −0.74, −1.15 and −1.85 V vs S.C.E. Bulk electrolysis of OMoV(OH)Pc (Pc2 = phthalocyanine dianion) shows that the first oxidation couple is due to the oxidation of the central MoV metal to MoVI and the first reduction couple due to reduction to OMoIVPc. Cyclic voltammetry and spectroelectrochemistry in DMSO also showed redox activity at the metal. Further reductions or oxidations in OMoVPc complexes occur at the phthalocyanine ring. OMoV(OH)Pc is readily photooxidized at the metal in the presence dichloromethane or dichlorobenzene, with the formation of OMoVIPc species.
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- Date Issued: 1994
Photoreduction of tin (IV) phthalocyanines
- Authors: Nyokong, Tebello
- Date: 1994
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293413 , vital:57083 , xlink:href="https://doi.org/10.1016/S0277-5387(00)83491-9"
- Description: Photolysis of Sn(IV)Pc(OH)2 (Pc = phthalocyanine dianion) and Sn(IV)Pc(Cl)2 using a tungsten lamp, and in the presence of SnCl2·2H2O as an electron donor results in the reduction of these complexes of π anion radical species. The reduction shows second order dependence on the concentration of the Sn(IV)Pc complexes and a first order dependence on SnCl2·H2O.
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- Date Issued: 1994
Redox reactions of an Mo (V) tetrasulfophthalocyanine
- Authors: Ferraudi, Guillermo , Nyokong, Tebello , Feliz, Mario , Perkovic, Marc , Rillema, D Paul
- Date: 1994
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/295530 , vital:57351 , xlink:href="https://doi.org/10.1016/0020-1693(93)03664-V"
- Description: The preparation of an Mo(V) tetrasulfophthalocyanine and some of its thermal and photochemical reactions have been investigated in this work. Electrochemical processes have been followed by means of the UVVis spectral changes and compared with those observed in flash photolysis. Mo(IV) and Mo(V)-ligand-radical species are common intermediates of the electrochemical and photochemical reactions. In 254 nm irradiations of the Mo(V) tetrasulfophthalocyanine in aqueous solutions of 2-propanol, the macrocycle can be photohydrogenated and the product of the photolysis can be reoxidized with O2 back to the parent complex.
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- Date Issued: 1994
Kinetics of the reaction of cyanide with ruthenium phthalocyanine complexes
- Authors: Nyokong, Tebello , Guthrie-Strachan, Jeffry
- Date: 1993
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/295509 , vital:57348 , xlink:href="https://doi.org/10.1016/S0020-1693(00)85128-2"
- Description: Kinetic studies of the reaction of cyanide with (CO)(DMF)RuPc and (DMSO)2RuPc in DMF are reported. In the presence of a large excess of cyanide, the (CN)2RuPc complex is formed by pseudo first order kinetics. The reaction is first order in both cyanide and phthalocyanine, with specific rate constants of 5.2×10−2 and 7.2×10−2 M−1 s−1 for reactions of cyanide with (CO)(DMF)RuPc and (DMSO)2RuPc, respectively. The rate constants correspond to the coordination of the second cyanide ligand to the ruthenium phthalocyanine species.
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- Date Issued: 1993
The nature of the oxidation products of dicyanoruthenium phthalocyanine in aqueous and non-aqueous solvents
- Authors: Nyokong, Tebello
- Date: 1993
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/295543 , vital:57352 , xlink:href="https://doi.org/10.1016/S0277-5387(00)81741-6"
- Description: The cyclic voltammetry of [(CN)2RuIIPc]2− in acetonitrile or dichloromethane shows two oxidation couples at E12 = 0.31 and 0.85 V (vs S.C.E.) in CH2Cl2 and E12 = 0.45 and 1.15 V (vs S.C.E.) in acetonitrile. The spectroelectrochemistry of [(CN)2RuIIPc]2− in these solvents showed that oxidations occur at the phthalocyanine ligand. K2[(CN)2RuIIPc] dissolves in water at pHs greater than 5. The cyclic voltammetry of this complex showed oxidation couples at 0.32 and 0.29 V (vs S.C.E.) for aqueous solutions containing sodium sulphate (0.1M) and for buffered solutions (pH = 9), respectively. Both cyclic voltammetry and controlled potential coulometry gave evidence of electrocrystallization of the oxidation product. Chemical oxidations of [(CN)2RuIIPc]2− in water also showed phthalocyanine ligand oxidation.
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- Date Issued: 1993