Electropolymerized Pyrrole-Substituted Manganese Phthalocyanine Films for the Electroassisted Biomimetic Catalytic Reduction of Molecular Oxygen
- Authors: Rodrigues, Nazaré Pereira , Obirai, Joe , Nyokong, Tebello , Bedioui, Fethi
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289372 , vital:56626 , xlink:href="https://doi.org/10.1002/elan.200403064"
- Description: We report for the first time on the electroassisted biomimetic activation of molecular oxygen by a newly prepared electropolymerized polypyrrole-manganese phthalocyanine film. The prepared films and their intervention in the electroassisted catalytic reduction of molecular oxygen were analyzed by cyclic voltammetry and UV-visible spectrophotometry on optically transparent electrodes. The obtained results demonstrate the probable existence of the key-steps responsible for the suggested formation of the highly reactive manganese oxo intermediate.
- Full Text:
- Date Issued: 2005
Estimating the potential role of commercial over-harvesting in resource viability: A case study of five useful tree species in South Africa
- Authors: Shackleton, Charlie M , Guthrie, G , Main, R
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/181324 , vital:43719 , xlink:href="https://doi.org/10.1002/ldr.652"
- Description: There is a growing commercialization of non-timber forest products (NTFPs) as a means of livelihood by rural communities throughout the developing world. This often occurs in the absence of any clear understanding of or guidelines regarding sustainable yields and ecological impacts, which may undermine the success of NTFP enterprises, especially from arid regions. This paper reports on the use of size class profiles and three quantitative indices to examine population profiles of five potentially useful tree species used as NTFPs in the semiarid lowveld of South Africa. We also contrast the population densities of the five tree species in 2003 with data from 1992. Low stem densities and population profiles indicated that three of the five species would preclude the establishment of NTFP enterprises based on their products. The other two species seem to have sufficient densities for some harvesting to take place, within an adaptive management framework. However, the longitudinal data indicated that the density of both these species had significantly declined over an eleven-year period, highlighting the need for appropriate management institutions. Additionally, the proportion of mature stems cut, and the degree of cutting per stem, had increased for all five species over the eleven years. The three quantitative indices of population stability were not correlated with one another, and hence provided a useful suite of measures sensitive to different aspects of size class profiles and their interpretation.
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- Date Issued: 2005
Melatonin generates singlet oxygen on laser irradiation but acts as a quencher when irradiated by lamp photolysis
- Authors: Maharaj, Deepa S , Molell, H , Antunes, Edith M , Maharaj, Hiren , Maree, D M , Nyokong, Tebello , Glass, Beverley D , Daya, Santy
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300335 , vital:57917 , xlink:href="https://doi.org/10.1111/j.1600-079X.2004.00185.x"
- Description: Melatonin, a naturally occurring chemical mediator, although assigned a diverse range of functions, has attracted interest in recent years because of its ability to function as a free radical scavenger. Because of the implications of singlet oxygen in neurotoxicity, the objective of the study was to investigate the ability of melatonin to quench singlet oxygen generated using laser irradiation or lamp photolysis. The results show that melatonin produces radicals upon laser irradation while the lamp photolysis studies show that melatonin is able to scavenge singlet oxygen produced by naphthalene. While melatonin is a free radical scavenger under biological conditions, it acts as a generator of singlet oxygen and or radicals (as ΦΔ is 1.41) when irradiated with laser light, implying that it has the potential to be used in photodynamic therapy in the destruction of tumors.
- Full Text:
- Date Issued: 2005
Self-Assembled Monolayers of Cobalt and Iron Phthalocyanine Complexes on Gold Electrodes
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello , Westbroek, Philippe
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/290363 , vital:56743 , xlink:href="https://doi.org/10.1002/elan.200302753"
- Description: The self-assembling of the octa(hydroxyethylthio)-metallophthalocyanine {MOHETPc (M=Co and Fe)} complexes and their similar analogues, octabutylthiometallophthalocyanine {MOBTPc (M=Co and Fe)} complexes on gold electrodes are investigated. Comparative surface voltammetric insights into their distinct self-assembling properties with respect to the passivation of Faradaic processes and surface coverages, including their solution electrochemistry, suggest different orientations and non-cleavage of their CS bonds. In the pH 2−9 range, the reversible [M(III)Pc(−2)]+ / [M(II)Pc(−2)] redox couples show potential shifts close to −59 mV / pH. The gold electrodes modified with the SAMs of these species show electrocatalytic activity towards the oxidation of thiols (L-cysteine, homocysteine and penicillamine) and thiocyanate in acidic media with detection limits in the region of 10−7–10−6 mol dm−3. These monolayers are stable and easily reproducible.
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- Date Issued: 2003
An assessment of the efficacy of two lysine microencapsulation techniques to determine the quantitative lysine requirement of the South African abalone, Haliotis midae L
- Authors: Shipton, Thomas A , Britz, Peter J , Walker, Roderick B
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184289 , vital:44197 , xlink:href="https://doi.org/10.1046/j.1365-2095.2002.00204.x"
- Description: The quantification of the essential amino acid requirements of a species is a prerequisite to the formulation of biologically optimized diets. In this study, crystalline L-lysine was used in an attempt to determine the quantitative lysine requirement of juvenile Haliotis midae. Two microencapsulation techniques [gelatine/acacia and cellulose acetate phthalate (CAP)] were used to retard leaching of crystalline L-lysine incorporated into semipurified test diets. An assessment of the efficacy of the encapsulation techniques, revealed that despite effective lysine supplementation, H. midae fed semipurified test diets containing encapsulated crystalline L-lysine failed to promote significant improvements in either growth, feed or protein efficiency (P > 0.05). The failure of the crystalline L-lysine to illicit growth and nutritional responses is discussed.
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- Date Issued: 2002
Melatonin protects against copper‐mediated free radical damage
- Authors: Parmar, Paresh , Limson, Janice L , Nyokong, Tebello , Daya, Santy
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289617 , vital:56654 , xlink:href=" https://doi.org/10.1034/j.1600-079X.2002.01859.x"
- Description: Copper is an essential trace element which forms an integral component of many enzymes. While trace amounts of copper are needed to sustain life, excess copper is extremely toxic. Copper has been implicated in various neurodegenerative disorders, such as Wilson's and Alzheimer's diseases. Previous studies showed that melatonin, the principle secretory product of the pineal gland, binds Cupric chloride (Cu2+) and that this may have implications in copper-induced neurodegenerative diseases. In the present study, in vitro copper-mediated lipid peroxidation was induced. Melatonin (5 mM) protected against copper-mediated lipid peroxidation in liver homogenates. Electron micrographs of in vivo administered Cu2+ and melatonin show that melatonin affords some protection to rat hepatocytes in the presence of copper. Electrochemical studies performed show that melatonin, in addition to binding Cu2+, may provide protection against copper-mediated free radical damage by binding Cu1+. The findings of these studies provide further evidence for the neuroprotective role of melatonin.
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- Date Issued: 2002
The identification of the UV degradants of melatonin and their ability to scavenge free radicals
- Authors: Maharaj, Deepa S , Anoopkumar-Dukie, Shailendra , Glass, Beverley D , Antunes, Edith M , Lack, Barbara A , Walker, Roderick B , Daya, Santylal
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184303 , vital:44198 , xlink:href="https://doi.org/10.1034/j.1600-079X.2002.01866.x"
- Description: Ultraviolet (UV) light is known to induce the generation of free radicals in biological tissues such as skin. Of these free radicals, the O2–· and particularly the ·OH radical can induce cellular damage including lipid peroxidation. Thus, the use of antioxidants to prevent such damage induced by UV irradiation has received much attention recently. One such antioxidant, which has the potential to be incorporated into sunscreens, is the pineal secretory product melatonin. One of the concerns of using melatonin in sunscreens is its photostability. In the present study, we investigated the photostability of melatonin subjected to UV irradiation. In addition, we used liquid chromatography mass spectrometry (LC-MS) to identify the degradants and we also assessed the ability of the degradants to inhibit O2–· generation as well as lipid peroxidation in rat brain homogenate. The results show that UV irradiation of melatonin (0.1 mg/mL) using a 400-W lamp for 2 hr caused a significant decline of melatonin to 18% of its original concentration after 20 min, with the decline continuing until the melatonin concentration reaches zero at 120 min. The LC-MS results show that the degradants of melatonin are 6-hydroxymelatonin and N1-acetyl-N2-formyl-5-methoxykynurenamine (AFMK). These degradants were able to provide equipotent activity against potassium cyanide (KCN)-induced superoxide generation compared to non-irradiated melatonin. Thus, the study shows that although melatonin is rapidly degraded by UV irradiation, the degradants retain antioxidant activity, making melatonin a likely candidate for inclusion in sunscreens.
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- Date Issued: 2002
Voltammetric detection of vitamin B1 at carbon paste electrodes and its determination in tablets
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289692 , vital:56663 , xlink:href="https://doi.org/10.1002/1521-4109(200209)14"
- Description: The voltammetric behavior of vitamin B1 in alkaline medium at carbon paste electrode (CPE) is discussed. A method based on cyclic voltammetry for the determination of vitamin B1 at carbon paste electrode modified with manganese phthalocyanine (MnPc-CPE) is presented. In pH 10 buffer, the modified electrode showed catalytic activity towards the oxidation of vitamin B1 by considerably increasing the oxidation current of one of the observed waves compared to the oxidation current obtained at an unmodified electrode. The modified electrode was stable towards the determination of vitamin B1 compared to the unmodified electrode that is completely poisoned after a few scans. A linear relationship between the oxidation current and the concentration of vitamin B1 in solution was observed. The detection limit for vitamin B1 at the modified electrode was of the order of 10−5 mol dm−3. Commercial vitamin B1 tablets were analyzed using the modified electrodes.
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- Date Issued: 2002
Voltammetric detection of vitamin B1 at carbon paste electrodes and its determination in tablets
- Authors: Oni, Joshua , Westbroek, Philippe , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289678 , vital:56662 , xlink:href="https://doi.org/10.1002/1521-4109(200209)14"
- Description: The voltammetric behavior of vitamin B1 in alkaline medium at carbon paste electrode (CPE) is discussed. A method based on cyclic voltammetry for the determination of vitamin B1 at carbon paste electrode modified with manganese phthalocyanine (MnPc-CPE) is presented. In pH 10 buffer, the modified electrode showed catalytic activity towards the oxidation of vitamin B1 by considerably increasing the oxidation current of one of the observed waves compared to the oxidation current obtained at an unmodified electrode. The modified electrode was stable towards the determination of vitamin B1 compared to the unmodified electrode that is completely poisoned after a few scans. A linear relationship between the oxidation current and the concentration of vitamin B1 in solution was observed. The detection limit for vitamin B1 at the modified electrode was of the order of 10−5 mol dm−3. Commercial vitamin B1 tablets were analyzed using the modified electrodes.
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- Date Issued: 2002
Interaction of serotonin and melatonin with sodium, potassium, calcium, lithium and aluminium
- Authors: Lack, Barbara , Daya, Santy , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291553 , vital:56886 , xlink:href="https://doi.org/10.1034/j.1600-079x.2001.310202.x"
- Description: In the present study, we investigated the ability of serotonin and melatonin to bind metals that occur naturally in the brain. An electrochemical technique called adsorptive cathodic stripping voltammetry (AdCSV) was employed to study the metal–serotonin or metal–melatonin interactions. The results show that both serotonin and melatonin form stable complexes with lithium and potassium, with serotonin favouring lithium over potassium, and melatonin favouring potassium over lithium. Coordination between either serotonin or melatonin and calcium was not favoured. The stability of the complexes formed between serotonin and the metals decreased with the metals as follows: Li+>K+>Al3+>Na+>Ca2+. The trend for melatonin–metal complexes was K+>Li+>Na+>Al3+>Ca2+. The binding and stable complex formation between both ligands, serotonin and melatonin with lithium, potassium and sodium is of biological importance. The binding of serotonin to lithium could provide an explanation for the therapeutic effects of lithium in depression treatment, whereas the binding of aluminium by melatonin could provide insight into the role of this element in the aetiology of Alzheimer's disease.
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- Date Issued: 2001
The effect of variations in pH and temperature on stability of melatonin in aqueous solution
- Authors: Daya, Santylal , Walker, Roderick B , Glass, Beverley D , Anoopkumar-Dukie, Shailendra
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184314 , vital:44207 , xlink:href="https://doi.org/10.1034/j.1600-079x.2001.310209.x"
- Description: Melatonin (N-acetyl-5-methoxytryptamine) has a diverse range of functions, including the control of neuroendocrine events. A number of studies have shown that melatonin may be of potential benefit for the treatment of insomnia, as well as neurodegenerative disorders. At present, there are numerous dosage forms of melatonin, with the oral route of administration being most popular. Presently, there is little information on the stability of melatonin over a pH range. With the changes in pH in the gastro-intestinal tract, as well as in different experimental conditions, information on the stability of melatonin would be important. We used a high-performance liquid chromatography method to determine the stability of melatonin solutions over a pH range (1.2–12) at room temperature and at 37°C over a period of 21 days. The results show that no melatonin degradation occurred in the first 2 days. From days 3 to 21, there was a gradual decline in melatonin at all pHs, with the decline not exceeding 30%. No decline in melatonin levels occurred in the first 2 days at 37°C. From days 3 to 21, melatonin levels declined gradually, with the decline not exceeding 29%.
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- Date Issued: 2001
Interaction of the neurotransmitter acetylcholine with aluminium, calcium and sodium
- 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.
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- Date Issued: 2000
Melatonin alters the photodegradation of paracetamol
- Authors: Anoopkumar-Dukie, Shailendra , Glass, Beverley D , Walker, Roderick B , Daya, Santylal
- Date: 2000
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184357 , vital:44211 , xlink:href="https://doi.org/10.1211/146080800128735755"
- Description: The effects of melatonin, a known free-radical scavenger, on paracetamol in the presence of UV irradiation was studied by use of HPLC. The experiments were performed in air and nitrogen. The results show that the rate of photodegradation of melatonin is faster in air than in nitrogen whereas that of paracetamol is similar in air and nitrogen. When the two drugs were combined, melatonin retarded the degradation of paracetamol for up to 6h in the presence of nitrogen. However, in the presence of air melatonin rapidly enhances the photodegradation of paracetamol. This study shows that a combination of melatonin and paracetamol in the presence of air and UV irradiation can lead to rapid inactivation of both agents, thus raising important concerns about the possible use of melatonin as sunscreen
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- Date Issued: 2000
The interaction of melatonin and its precursors with aluminium, cadmium, copper, iron, lead, and zinc
- Authors: Limson, Janice L , Nyokong, Tebello , Daya, Santy
- Date: 1998
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293323 , vital:57075 , xlink:href="https://doi.org/10.1111/j.1600-079X.1998.tb00361.x"
- Description: Melatonin, a pineal secretory product, and its precursors, tryptophan and serotonin, were examined for their metal binding affinities for both essential and toxic metals: aluminium, cadmium, copper, iron, lead, and zinc. An electrochemical technique, adsorptive stripping voltammetry, showed the varying abilities of melatonin and its precursors to bind the metals in situ. The results show that the following metal complexes were formed: aluminium with melatonin, tryptophan, and serotonin; cadmium with melatonin and tryptophan; copper with melatonin and serotonin; iron(III) with melatonin and serotonin; lead with melatonin, tryptophan, and serotonin; and zinc with melatonin and tryptophan. Iron(II) showed the formation of an in situ complex with tryptophan only. These studies suggest a further role for melatonin in the reduction of free radical generation and metal detoxification, and they may explain the accumulation of aluminium in Alzheimer's disease.
- Full Text:
- Date Issued: 1998
Catalytic behavior of osmium (II), rhodium (III) and ruthenium (II) Phthalocyanines towards the electrooxidation of cysteine on glassy carbon electrodes
- Authors: Sekota, Mantoa , Nyokong, Tebello
- Date: 1997
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293290 , vital:57072 , xlink:href=" https://doi.org/10.1002/elan.1140091608"
- Description: Glassy carbon electrodes (GCE's) modified with phthalocyanine complexes of Rh, Ru and Os are employed for the catalytic oxidation of cysteine. When cyanide and dimethylsulfoxide (DMSO) are used as axial ligands giving (DMSO)(Cl)RhIIIPc, [(CN)2RhIIIPc]−, (DMSO)2OsPcII, and [(DMSO)2Ru(II)Pc]·2DMSO complexes, the peak currents for the oxidation of cysteine increase after each scan, indicating an increase in the catalytic activity of the electrode with repetitive scanning. This improvement in the catalytic activity of the GCE after the first scan is attributed to the formation of dimeric π cation radical species at the electrode surface.
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- Date Issued: 1997
Voltammetric behavior of cysteine and metallothionein on cobalt (II) tetrasulfonated phthalocyanine modified glassy carbon electrodes
- Authors: Limson, Janice L , Nyokong, Tebello
- Date: 1997
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293346 , vital:57077 , xlink:href="https://doi.org/10.1002/elan.1140090314"
- Description: Cysteine, and rat Cd, Zn-metallothionein (Cd, Zn-MT) have been studied electrochemically at glassy carbon electrodes modified with cobalt(II) tetrasulfonated phthalocyanine, [CoIITSPc]4−, where Pc(2-) = phthalocyanine dianion. The electrode was modified by electrodeposition of [CoIITSPc]4−. The anodic currents for the oxidation of cysteine on these electrodes are observed at 0.82 V (vs. Ag/AgCl) in acidic media. The anodic currents for the oxidation of Cd, Zn-MT are observed at 0.90 V at pH 8.4 (Tris buffer).
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- Date Issued: 1997