SA scientist one of the top five female physical scientists

South African scientist Professor Tebello Nyokong scoops 2009 L’ORÉAL-UNESCO For Women in Science Award. Announced on November 10, South African scientist Professor Tebello Nyokong has become the first South African scientist to win the L’ORÉALUNESCO award for women in science for research in physical sciences

Curiosity first, applications later

Tebello Nyokong speaks to Robert Berold and Janice Limson about her career as a chemist. Tebello Nyokong, who holds a research chair in medicinal chemistry and nanotechnology at Rhodes University, has become the first South African scientist to win the L’Oreal-UNESCO award for women in science, in the physical sciences. Only one laureate is selected from each of five world regions, and Nyokong is the 2009 laureate for Africa and the Arab states. She and the winners from the other four regions travel to Paris in March to each accept the award and a generous prize of close to R1 million. Nyokong now heads the new Nanotechnology Innovation Centre for medical sensors: the biggest single research investment in the history of Rhodes. Linked to other nanotechnology centres in the country, it is designed to bridge the gap between research and the market

Rhodes University Chemistry Professor Tebello Nyokong Receives The 2009 L'oreal-Unesco Award For Women In Science

Professor Tebella Nyokong has become the first South African scientist to win the L'OREAL-UNESCO award for women in science, for physical sciences. The awards honour exceptional women in science. Each year one laureate is selected from five world regions. Professor Nyokong is the laureate for Africa and the Arab states for 2009

Electrochemical studies of metal-ligand interactions and of metal binding proteins

Electrochemical methods were researched for the analysis of metals, proteins and the identification of metal binding proteins. Adsorptive cathodic stripping voltamrnetry for metal analysis combines the inherent sensitivity of electrochemical techniques with the specificity of ligands for the nonfaradaic preconcentration of analytes at the electrode. The utility of catechol, resorcinol, 4-methylcatechol and 4-t-butylcatechol as ligands was explored for the sensitive analysis of copper, bismuth, cadmium and lead on a mercury film glassy carbon electrode. Metal complexes of lead, copper and bismuth with resorcinol showed the largest increase in current with increase in metal concentration, whereas complexes of these metals with 4-t-butylcatechol showed the lowest current response. Cadmium showed the highest current responses with 4-methylcatechol. The four metals could be determined simultaneously in the presence of resorcinol, although considerable interference was observed between bismuth and copper. The electroanalysis of cysteine and cysteine containing proteins at carbon electrodes are impaired by slow electron transfer rates at carbon electrodes, exhibiting high overpotentials, greater than 1 V vs Ag! Agel. Metallophthalocyanines have been shown to promote the electrocatalysis of cysteine at lowered potentials. Chemical modification of electrodes with appropriate modifiers is a means of incorporating specificity into electroanalysis, with applications in electrocatalysis. A glassy carbon electrode was modified by electrodeposition of cobalt (II) tetrasulphophthalocyanine [Co(II)TSPct to produce a chemically modified glassy carbon electrode (CMGCE). The CoTSPc-CMGCE catalysed the oxidation of cysteine in the pH range 1 to 10. The significance of this electrode is an application for analysis of proteins at biological pH's. A biscyanoruthenium(II) phthalocyanine CMGCE catalysed the oxidation of cysteine at 0.43 V vs Ag/AgCl a significant lowering in the overpotential for the oxidation of cysteine. Metallothionein, a metal binding protein, is believed to be involved in metal homeostasis and detoxification in the peripheral organs of living systems. A method for the quantitative determination of this protein utilising its high cysteine content was presented. At pH 8.4 Tris-HCl buffer, and using a CoTSPc-CMGCE modified by electrodeposition of the modifier, the anodic peaks for the oxidation of metallothionein was observed at 0. 90 V vs Ag/ AgCI. Ferredoxin is a simple iron-sulphur protein. One tenth of its residues are cysteine. Ferredoxin is involved in simple electron transfer processes during photosynthesis and respiration. Electrochemical studies of spinach ferredoxin were conducted at a CoTSPc-CMGCE. Anodic currents for the oxidation of the cysteine fragment of ferredoxin was observed at 0.85 V vs Ag/AgCl in HEPES buffer at pH 7.4, representing a new method for analysis of this protein. Voltammetric studies of its ferric/ferrous transition have shown quasi-reversible waves atE~ -0.62 V vs Ag/AgCl only in the presence of promoters. At a CoTSPc-CMGCE, a cathodic wave attributed to the reduction of Fe(III)/Fe(II) was observed at Epc -0.34 V vs Ag/AgCl. This represents an alternative method for voltammetric studies of the ferric/ferrous transition at significantly lowered potentials. Melatonin, a pineal gland hormone functions m setting and entraining circadian rhythms and in neuroprotection as a free radical scavenger and general antioxidant. Using adsorptive cathodic stripping voltammetry, the binding affinities of melatonin, serotonin and tryptophan for metals, were measured. The results showed that the following metal complexes were formed: aluminium with melatonin, serotonin and tryptophan; cadmium with melatonin and tryptophan; copper with melatonin and serotonin; iron (III) with melatonin and serotonin; lead with melatonin, tryptophan and serotonin, zinc with melatonin and tryptophan and iron (II) with tryptophan. The studies suggest a further role for melatonin in the reduction of free radical generation and in metal detoxification and may explain the accumulation of aluminium in Alzheimer's disease

Electrochemical studies of metal-ligand interactions and of metal binding proteins

Electrochemical methods were researched for the analysis of metals, proteins and the identification of metal binding proteins. Adsorptive cathodic stripping voltamrnetry for metal analysis combines the inherent sensitivity of electrochemical techniques with the specificity of ligands for the nonfaradaic preconcentration of analytes at the electrode. The utility of catechol, resorcinol, 4-methylcatechol and 4-t-butylcatechol as ligands was explored for the sensitive analysis of copper, bismuth, cadmium and lead on a mercury film glassy carbon electrode. Metal complexes of lead, copper and bismuth with resorcinol showed the largest increase in current with increase in metal concentration, whereas complexes of these metals with 4-t-butylcatechol showed the lowest current response. Cadmium showed the highest current responses with 4-methylcatechol. The four metals could be determined simultaneously in the presence of resorcinol, although considerable interference was observed between bismuth and copper. The electroanalysis of cysteine and cysteine containing proteins at carbon electrodes are impaired by slow electron transfer rates at carbon electrodes, exhibiting high overpotentials, greater than 1 V vs Ag! Agel. Metallophthalocyanines have been shown to promote the electrocatalysis of cysteine at lowered potentials. Chemical modification of electrodes with appropriate modifiers is a means of incorporating specificity into electroanalysis, with applications in electrocatalysis. A glassy carbon electrode was modified by electrodeposition of cobalt (II) tetrasulphophthalocyanine [Co(II)TSPct to produce a chemically modified glassy carbon electrode (CMGCE). The CoTSPc-CMGCE catalysed the oxidation of cysteine in the pH range 1 to 10. The significance of this electrode is an application for analysis of proteins at biological pH's. A biscyanoruthenium(II) phthalocyanine CMGCE catalysed the oxidation of cysteine at 0.43 V vs Ag/AgCl a significant lowering in the overpotential for the oxidation of cysteine. Metallothionein, a metal binding protein, is believed to be involved in metal homeostasis and detoxification in the peripheral organs of living systems. A method for the quantitative determination of this protein utilising its high cysteine content was presented. At pH 8.4 Tris-HCl buffer, and using a CoTSPc-CMGCE modified by electrodeposition of the modifier, the anodic peaks for the oxidation of metallothionein was observed at 0. 90 V vs Ag/ AgCI. Ferredoxin is a simple iron-sulphur protein. One tenth of its residues are cysteine. Ferredoxin is involved in simple electron transfer processes during photosynthesis and respiration. Electrochemical studies of spinach ferredoxin were conducted at a CoTSPc-CMGCE. Anodic currents for the oxidation of the cysteine fragment of ferredoxin was observed at 0.85 V vs Ag/AgCl in HEPES buffer at pH 7.4, representing a new method for analysis of this protein. Voltammetric studies of its ferric/ferrous transition have shown quasi-reversible waves atE~ -0.62 V vs Ag/AgCl only in the presence of promoters. At a CoTSPc-CMGCE, a cathodic wave attributed to the reduction of Fe(III)/Fe(II) was observed at Epc -0.34 V vs Ag/AgCl. This represents an alternative method for voltammetric studies of the ferric/ferrous transition at significantly lowered potentials. Melatonin, a pineal gland hormone functions m setting and entraining circadian rhythms and in neuroprotection as a free radical scavenger and general antioxidant. Using adsorptive cathodic stripping voltammetry, the binding affinities of melatonin, serotonin and tryptophan for metals, were measured. The results showed that the following metal complexes were formed: aluminium with melatonin, serotonin and tryptophan; cadmium with melatonin and tryptophan; copper with melatonin and serotonin; iron (III) with melatonin and serotonin; lead with melatonin, tryptophan and serotonin, zinc with melatonin and tryptophan and iron (II) with tryptophan. The studies suggest a further role for melatonin in the reduction of free radical generation and in metal detoxification and may explain the accumulation of aluminium in Alzheimer's disease

Substituted catechols as complexing agents for the determination of bismuth, lead, copper and cadmium by adsorptive stripping voltammetry

Copper, cadmium, lead and bismuth (> 5 μg ml−1) are determined by adsorptive cathodic stripping voltammetry (AdCSV) on a mercury film glassy carbon electrode, using catechol, 4-methylcatechol, 4-t-butylcatechol and resorcinol as complexing ligands. Complexes of lead, copper and bismuth with resorcinol showed the largest increase in current with increase in metal concentration, whereas complexes of these metals with 4-t-butylcatechol showed the lowest current response. Cadmium showed a different behaviour from the other three metals in that the highest current response was observed with 4-methylcatechol. The four metals could be determined simultaneously in the presence of resorcinol, although considerable interference was observed between bismuth and copper

Voltammetric behavior of cysteine and metallothionein on cobalt (II) tetrasulfonated phthalocyanine modified glassy carbon electrodes

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)

The interaction of melatonin and its precursors with aluminium, cadmium, copper, iron, lead, and zinc

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

The use of a quartz crystal microbalance with dissipation for the measurement of protein–protein interactions: a qualitative and quantitative analysis of the interactions between molecular chaperones

Biotechnology research and innovation depends on the ability to understand the molecular mechanisms of biological processes such as protein–protein and protein–ligand interactions. Surface plasmon resonance (SPR) spectroscopy is now well established as a quantitative technique for monitoring biomolecular interactions. In this study, we examined the recently developed quartz crystal microbalance with dissipation (QCM-D) method as an alternative to SPR spectroscopy to investigate protein–protein interactions, in particular, for chaperone–co-chaperone interactions. In mammalian cells, the Hsp70/Hsp90 organizing protein (Hop) is a co-chaperone required for the association of the molecular chaperones, heat shock protein 70 (Hsp70) and heat shock protein 90 (Hsp90). The objective of this research was to characterize qualitatively and quantitatively the interaction of Hsp70 with Hop. A truncated version of Hop consisting of only the C-terminal region and lacking the Hsp70-binding domain (GST-C-Hop) was used as a non-Hsp70- binding control. Immobilized GST-Hop was found to bind Hsp70 successfully, displaying a QCM-D response consistent with formation of a complex that became slightly more flexible as the concentration of bound Hsp70 increased. GST-C-Hop did not bind to Hsp70, thereby validating the specificity of the GST-Hop interaction with Hsp70. The kinetics of the interaction was followed at different concentrations of Hsp70, and an apparent thermodynamic dissociation constant (KD value) in the micromolar range was determined that correlated well with the value derived previously using SPR. This study represents a proof-of-principle that QCM-D can be applied to the analysis of chaperone–co-chaperone interactions. The economic and technical accessibility of QCM-D makes it a valuable tool for analyses of chaperone interactions, and protein– protein interactions in general

Application of carbon black and iron phthalocyanine composites in bioelectricity production at a brewery wastewater fed microbial fuel cell

Aerobic cathode microbial fuel cells (MFCs) have been widely researched to provide bioremediation of wastewaters, coupled to sustainable energy production. In order to effectively accomplish this aim, suitable catalysts and catalyst supports for oxygen reduction reaction (ORR) are required. While iron phthaloycanine (FePc), supported on multi-walled carbon nanotubes has previously been studied for this function, cost of industrial production may hinder this. Importantly, this study examines the use of several available grades of carbon black for their relative suitability to perform as supports for FePc in MFC formats. Voltammetric studies showed that the different grades of carbon black provided varying lowering of the ORR overpotential, between ∼160 and ∼270 mV relative to unmodified GCEs, and an optimum grade (N326) was selected for further study. Carbon black/FePC composite electrodes exhibited comparable lowering of the ORR overpotential (606 mV) to potentials previously reported to nanotube/FePc composites (620 mV), as well as lowered charge-transfer resistance compared to electrodes solely modified with FePc. When applied as cathode modifiers in dual chambered MFCs utilising Enterobacter cloacae, the combined use of carbon black and FePc provided greater power densities than either alone; composite electrodes obtaining ∼400% power density, compared to unmodified electrodes. Modification of the anode with carbon black further increased power density, generating power densities an order of magnitude larger than those obtained at unmodified electrodes. The ability of beer brewery waste water (BBWW) to generate power at these modified surfaces yielded permissible power densities (∼40% that of reinforced clostridial media). Differences observed, in particular under agitation, are attributed to variations in nutrient content and nutrient complexity, between the two fuel substrates