Comparative Spectroscopic and Electrochemical Properties of Bis (octakis (dodecylthio) naphthalocyaninato) europium (III) and Bis (tetra-tert-butylnaphthalocyaninato) europium (III) Complexes
- Nyokong, Tebello, Furuya, Fumio, Kobayashi, Nagao, Du, Daming, Liu, Wei, Jiang, Jianzhuang
- Authors: Nyokong, Tebello , Furuya, Fumio , Kobayashi, Nagao , Du, Daming , Liu, Wei , Jiang, Jianzhuang
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293174 , vital:57062 , xlink:href="https://doi.org/10.1021/ic990483b"
- Description: Bis(substituted-2,3-naphthalocyaninato)europium(III) complexes: bis(octakis(dodecylthio)-2,3-naphthalocyaninato)europium(III) {Eu[2,3-Nc(SC12H25)8]2, 1} and bis(tetra-tert-butyl-2,3-naphthalocyaninato)europium(III) {Eu[2,3-Nc(t-Bu)4]2, 2} have been synthesized by cyclic tetramerization of naphthalonitriles with Eu(acac)3·H2O in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in refluxing n-octanol. These compounds were characterized by UV−visible, magnetic circular dichroism (MCD), near-IR, IR, EPR, and mass spectroscopies. The absorption and MCD spectra of 1 showed splitting of the Q band, with peaks at 700 and 784 nm, red shifted from the Q band of 2 at 763 nm. The absorption and MCD spectral band deconvolution calculations of complex 1 gave two A terms in the Q-band region. The A terms are assigned to 2A2 → 2E1 transitions. Cyclic voltammograms of 1 and 2 showed reversible oxidation couples at E1/2 = −0.28 V (for 2) and −0.25 V (for 1) vs ferrocenium/ferrocene (Fc+/Fc). The second oxidation exhibited a complicated behavior for both complexes. The reduction couples for 2 were observed at E1/2 = −0.61, −1.64, −1.97, and −2.42 V, and for 1 they were observed at E1/2 = −0.62, −1.60, −1.86, and −2.27 V vs Fc+/Fc. Spectral changes observed on chemical oxidation and reduction of the complexes are presented, and the behaviors of 1 and 2 are compared.
- Full Text:
- Date Issued: 2000
- Authors: Nyokong, Tebello , Furuya, Fumio , Kobayashi, Nagao , Du, Daming , Liu, Wei , Jiang, Jianzhuang
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293174 , vital:57062 , xlink:href="https://doi.org/10.1021/ic990483b"
- Description: Bis(substituted-2,3-naphthalocyaninato)europium(III) complexes: bis(octakis(dodecylthio)-2,3-naphthalocyaninato)europium(III) {Eu[2,3-Nc(SC12H25)8]2, 1} and bis(tetra-tert-butyl-2,3-naphthalocyaninato)europium(III) {Eu[2,3-Nc(t-Bu)4]2, 2} have been synthesized by cyclic tetramerization of naphthalonitriles with Eu(acac)3·H2O in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in refluxing n-octanol. These compounds were characterized by UV−visible, magnetic circular dichroism (MCD), near-IR, IR, EPR, and mass spectroscopies. The absorption and MCD spectra of 1 showed splitting of the Q band, with peaks at 700 and 784 nm, red shifted from the Q band of 2 at 763 nm. The absorption and MCD spectral band deconvolution calculations of complex 1 gave two A terms in the Q-band region. The A terms are assigned to 2A2 → 2E1 transitions. Cyclic voltammograms of 1 and 2 showed reversible oxidation couples at E1/2 = −0.28 V (for 2) and −0.25 V (for 1) vs ferrocenium/ferrocene (Fc+/Fc). The second oxidation exhibited a complicated behavior for both complexes. The reduction couples for 2 were observed at E1/2 = −0.61, −1.64, −1.97, and −2.42 V, and for 1 they were observed at E1/2 = −0.62, −1.60, −1.86, and −2.27 V vs Fc+/Fc. Spectral changes observed on chemical oxidation and reduction of the complexes are presented, and the behaviors of 1 and 2 are compared.
- Full Text:
- Date Issued: 2000
Electrocatalytic behavior of substituted cobalt phthalocyanines towards the oxidation of cysteine
- Maree, Suzanne, Nyokong, Tebello
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293268 , vital:57070 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293268 , vital:57070 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
Electrocatalytic behavior of substituted cobalt phthalocyanines towards the oxidation of cysteine
- Maree, Suzanne, Nyokong, Tebello
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293185 , vital:57063 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293185 , vital:57063 , xlink:href="https://doi.org/10.1016/S0022-0728(00)00281-3"
- Description: Ring substituted cobalt phthalocyanine complexes of the form CoPc(X)4, (where X=NH2, NO2, C(CH3)3, SO3H and COOH) are compared for their catalytic activities towards the oxidation of cysteine. The potential for the electrocatalytic oxidation of cysteine is closely related to the CoIII/CoII couple of the CoPc(X)4 complexes in acidic media and to the CoII/CoI couple in basic media. The catalytic currents and the oxidation potential for cysteine are dependent on the pH of the solution, the potential becoming less positive as the pH increases and the catalytic currents decreasing with increase in pH, for the same concentration of cysteine. The magnitudes of the catalytic currents (after ten scans) for cysteine oxidation at pH 8.3 and on electrodes modified with the CoPc(X)4 complexes increased with the nature of the ring substituent as follows: NO2 less than NH2 less than SO3H less than C(CH3)3 less than COOH.
- Full Text:
- Date Issued: 2000
Electrocatalytic properties of vitamin B12 towards oxidation and reduction of nitric oxide
- Vilakazi, Sibulelo Lea, Nyokong, Tebello
- Authors: Vilakazi, Sibulelo Lea , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293196 , vital:57064 , xlink:href="https://doi.org/10.1016/S0013-4686(00)00628-9"
- Description: This paper reports on the catalytic behaviour of cyanocobalamin (VB12) towards the reduction and oxidation of nitric oxide. When VB12 is adsorbed on glassy carbon electrodes, it catalyses the reduction of nitric oxide (NO) in pH 4 and 9 buffers. In the absence of NO, cyclic voltammetry shows that VB12 is reduced by a one-step two-electron reduction from CoIII to the CoI species. Addition of NO at pH 9 to solutions of VB12 resulted in the splitting of the cyclic voltammetry peaks as a result of a consecutive one-electron reduction of the central CoIII metal in VB12 to CoII and finally to CoI. The catalytic peak for oxidation of NO on a glassy carbon electrode modified with VB12 was observed at 1.21 V versus Ag∣AgCl, at pH 9. The products of the catalytic reduction of nitric oxide include ammonia and hydroxylamine.
- Full Text:
- Date Issued: 2000
- Authors: Vilakazi, Sibulelo Lea , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293196 , vital:57064 , xlink:href="https://doi.org/10.1016/S0013-4686(00)00628-9"
- Description: This paper reports on the catalytic behaviour of cyanocobalamin (VB12) towards the reduction and oxidation of nitric oxide. When VB12 is adsorbed on glassy carbon electrodes, it catalyses the reduction of nitric oxide (NO) in pH 4 and 9 buffers. In the absence of NO, cyclic voltammetry shows that VB12 is reduced by a one-step two-electron reduction from CoIII to the CoI species. Addition of NO at pH 9 to solutions of VB12 resulted in the splitting of the cyclic voltammetry peaks as a result of a consecutive one-electron reduction of the central CoIII metal in VB12 to CoII and finally to CoI. The catalytic peak for oxidation of NO on a glassy carbon electrode modified with VB12 was observed at 1.21 V versus Ag∣AgCl, at pH 9. The products of the catalytic reduction of nitric oxide include ammonia and hydroxylamine.
- Full Text:
- Date Issued: 2000
Interaction between iron (II) tetrasulfophthalocyanine and the neurotransmitters, serotonin and dopamine
- Oni, Joshua, Nyokong, Tebello
- Authors: Oni, Joshua , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293223 , vital:57066 , xlink:href="https://doi.org/10.1016/S0277-5387(00)00421-6"
- Description: This work reports on the kinetics of interaction of iron(II) tetrasulfophthalocyanine, [FeTSPc]4−, with dopamine (DA) and serotonin (5-HT). The interaction results in the coordination of dopamine and serotonin to [FeTSPc]4−, followed by internal electron transfer and the formation of [(DA+)FeITSPc]4− and [(5-HT+) FeITSPc]4− complexes, respectively. The rate constants for the coordination of dopamine or serotonin to [FeTSPc]4− and the formation of the FeITSPc species were found to be kf=6.8 and 9.3 dm3 mol−1 s−1, respectively. The equilibrium constants were 2.2×103 and 1.5×103 dm3 mol−1, respectively, for the interaction of dopamine or serotonin to [FeTSPc]4−.
- Full Text:
- Date Issued: 2000
- Authors: Oni, Joshua , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293223 , vital:57066 , xlink:href="https://doi.org/10.1016/S0277-5387(00)00421-6"
- Description: This work reports on the kinetics of interaction of iron(II) tetrasulfophthalocyanine, [FeTSPc]4−, with dopamine (DA) and serotonin (5-HT). The interaction results in the coordination of dopamine and serotonin to [FeTSPc]4−, followed by internal electron transfer and the formation of [(DA+)FeITSPc]4− and [(5-HT+) FeITSPc]4− complexes, respectively. The rate constants for the coordination of dopamine or serotonin to [FeTSPc]4− and the formation of the FeITSPc species were found to be kf=6.8 and 9.3 dm3 mol−1 s−1, respectively. The equilibrium constants were 2.2×103 and 1.5×103 dm3 mol−1, respectively, for the interaction of dopamine or serotonin to [FeTSPc]4−.
- Full Text:
- Date Issued: 2000
Interaction of nitric oxide with cobalt (II) tetrasulfophthalocyanine
- Vilakazi, Sibulelo, Nyokong, Tebello
- Authors: Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293235 , vital:57067 , xlink:href="https://doi.org/10.1016/S0277-5387(99)00373-3"
- Description: The interaction of nitric oxide (NO) with cobalt(II) tetrasulfophthalocyanine [Co(II)TSPc]4−) has been studied. Coordination of NO is accompanied by electron transfer from the central metal in [Co(II)TSPc]4−, the resulting complex being represented as [(NO−)Co(III)TSPc]4−. The rate constant for the formation of this species is kf=142±7 dm3 mol−1 s−1 and an equilibrium constant of 3.0±0.5×105 dm3 mol−1 was obtained. When adsorbed to a glassy carbon electrode, [Co(II)TSPc]4− catalyses the oxidation and reduction of NO, with a detection limit of the order of 10−9 mol dm−3. Ammonia and hydroxylamine are some of the reduction products obtained for the reduction of NO on [Co(II)TSPc]4−-modified glassy carbon electrodes.
- Full Text:
- Date Issued: 2000
- Authors: Vilakazi, Sibulelo , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293235 , vital:57067 , xlink:href="https://doi.org/10.1016/S0277-5387(99)00373-3"
- Description: The interaction of nitric oxide (NO) with cobalt(II) tetrasulfophthalocyanine [Co(II)TSPc]4−) has been studied. Coordination of NO is accompanied by electron transfer from the central metal in [Co(II)TSPc]4−, the resulting complex being represented as [(NO−)Co(III)TSPc]4−. The rate constant for the formation of this species is kf=142±7 dm3 mol−1 s−1 and an equilibrium constant of 3.0±0.5×105 dm3 mol−1 was obtained. When adsorbed to a glassy carbon electrode, [Co(II)TSPc]4− catalyses the oxidation and reduction of NO, with a detection limit of the order of 10−9 mol dm−3. Ammonia and hydroxylamine are some of the reduction products obtained for the reduction of NO on [Co(II)TSPc]4−-modified glassy carbon electrodes.
- Full Text:
- Date Issued: 2000
Interaction of the neurotransmitter acetylcholine with aluminium, calcium and sodium
- Matlaba, Pulane M, Daya, Santy, Nyokong, Tebello
- Authors: Matlaba, Pulane M , Daya, Santy , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293246 , vital:57068 , xlink:href="https://doi.org/10.1211/146080800128735890"
- Description: Binding of aluminium to acetylcholine has important biological implications particularly in Alzheimer's disease. An electrochemical technique, adsorptive cathodic stripping voltammetry, has been employed in this study to investigate the in-situ formation of a complex between aluminium and acetylcholine. The stability of the resulting complex was compared with that of the in-situ complexes formed between acetylcholine and sodium or calcium. From the shifts in the reduction potential of the metals on addition of acetylcholine it is concluded that a strong complex is formed between acetylcholine and aluminium. Much weaker complexes are formed between calcium or sodium and acetylcholine. These results have important implications in the aetiology of Alzheimer's disease-in which brain aluminium concentrations are known to be high and brain cholinergic function is lower than normal.
- Full Text:
- Date Issued: 2000
- Authors: Matlaba, Pulane M , Daya, Santy , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293246 , vital:57068 , xlink:href="https://doi.org/10.1211/146080800128735890"
- Description: Binding of aluminium to acetylcholine has important biological implications particularly in Alzheimer's disease. An electrochemical technique, adsorptive cathodic stripping voltammetry, has been employed in this study to investigate the in-situ formation of a complex between aluminium and acetylcholine. The stability of the resulting complex was compared with that of the in-situ complexes formed between acetylcholine and sodium or calcium. From the shifts in the reduction potential of the metals on addition of acetylcholine it is concluded that a strong complex is formed between acetylcholine and aluminium. Much weaker complexes are formed between calcium or sodium and acetylcholine. These results have important implications in the aetiology of Alzheimer's disease-in which brain aluminium concentrations are known to be high and brain cholinergic function is lower than normal.
- Full Text:
- Date Issued: 2000
Photocatalytic properties of neodymium diphthalocyanine towards the transformation of 4-chlorophenol
- Nensala, Ngudiankama, Nyokong, Tebello
- Authors: Nensala, Ngudiankama , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/${Handle} , vital:58491 , xlink:href="https://doi.org/10.1016/S1381-1169(00)00283-1"
- Description: Photolysis of aqueous solutions of 4-chlorophenol (4-Cp) in the presence of solid neodymium diphthalocyanine ([Pc(−2)NdPc(−2)]−) and oxygen using visible and ultraviolet (UV) radiation resulted in the formation of a number of products. For photolysis in the visible region, phenol, benzoquinone, hydroquinone were observed as intermediates and 4-chlorocatechol (4-CC) as the main product; intermediates similar to those observed for visible photolysis were obtained. Langmuir–Hinshelwood kinetic model was used for treatment of photochemical data.
- Full Text:
- Date Issued: 2000
Photocatalytic properties of neodymium diphthalocyanine towards the transformation of 4-chlorophenol
- Authors: Nensala, Ngudiankama , Nyokong, Tebello
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/${Handle} , vital:58491 , xlink:href="https://doi.org/10.1016/S1381-1169(00)00283-1"
- Description: Photolysis of aqueous solutions of 4-chlorophenol (4-Cp) in the presence of solid neodymium diphthalocyanine ([Pc(−2)NdPc(−2)]−) and oxygen using visible and ultraviolet (UV) radiation resulted in the formation of a number of products. For photolysis in the visible region, phenol, benzoquinone, hydroquinone were observed as intermediates and 4-chlorocatechol (4-CC) as the main product; intermediates similar to those observed for visible photolysis were obtained. Langmuir–Hinshelwood kinetic model was used for treatment of photochemical data.
- Full Text:
- Date Issued: 2000
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