Role of the Relaxation of the Iron(ll1) Ion Spin States Equilibrium in the Kinetics of Ligand Binding to Methaemoglobin

Temperature-jump experiments of the reaction of the thiocyanate ion with human aquomethaemoglobin have been performed in the presence of a 10-fold excess of inositol hexakisphosphate (inositolP,). Two kinetic phases corresponding to the a and /3 subunits were observed. Kinetic parameters of the reaction were evaluated from the reciprocal relaxation times on the basis of a fast relaxation of the iron(iii) ion spin states equilibrium before binding of the ligand. The association, ki,, and dissociation, k-i,, rate constants determined were: k,, = 225 dm3 mol-' s-', k-aL = 1.52 s-', k,, = 2430 dm3 mol-' s-', k-pL = 6.51 s-' at 27"C, pH 6.44. There was good agreement between the equilibrium constant of the ligand binding step determined by static methods (Kequ = 204 & 11 dm3 mol-') and that evaluated from kinetic data [(KaLKpL)1'2 = 235 & 12 dm3 mol-'1. The value ksJkaL = 11 obtained ensured proper separation of the two kinetic phases. Analyses of the subunit relaxation amplitudes, a€,, , showed that inositolP, perturbed the absorption spectrum of the /3 subunits. This suggests that in the presence of the organic phosphate, methaemoglobin behaves as a protein with independent binding sites rather than as an allosteric molecule. The kinetic and relaxation amplitude spectral characteristics of the subunits, in the presence of inositolP, have demonstrated that the kinetic dynamics are effectively decoupled in a stable tetramer

Relaxation amplitude analysis of thiocyanate and formate binding to human aquomethemoglobin A

The kinetics of the reaction of thiocyanate and formate ions with aquomethemoglobin can be adequately accounted for by a scheme in which the ligand-binding step in both the alpha and beta subunits is preceded by a fast transition of the iron atom from high to low spin (Okonjo, K.O. (1980) Eur. J. Biochem. 105, 329-334). Amplitude expressions derived from this scheme are used to analyse the relaxation amplitude data for alpha and beta subunits within the methemoglobin tetramer. The mean of the reaction enthalpies for ligand binding by the subunits within the tetramer is in good agreement with the reaction enthalpy for ligand binding by the methemoglobin tetramer obtained from a Van't Hoff plot of equilibrium titration data

Subunit iron spin heterogeneity in human aquomethemoglobin A

On the basis of a reaction scheme in which the ligand binding steps are preceded by fast iron spin transitions (Okonjo, K.O. (1980) Eur. J. Biochem. 105, 329-334; Iwuoha, E.I. and Okonjo, K.O. (1985) Biochim. Biophys. Acta 829, 327-334), the spin equilibrium constants of methemoglobin subunits are calculated from kinetic and equilibrium binding parameters with azide ion as ligand. The results demonstrate the existence of thermodynamic spin heterogeneity within the tetramer

Levels of selected heavy metals in some brands of Cigarettes marketed in University of Port Harcourt, Rivers State.

Four commonly smoked brands cigarette from Abuja campus in the University of Port Harcourt were randomly sampled and analyzed for heavy metals using Atomic Adsorption Spectrometry (AAS). The brands include Benson and Hedges, Rothmans, Dorchester, and St. Moritz. The results of the analysis indicated that the concentration of Zn was found to be in range of 27.48-64.29mgkg-1, Cu had 11.27-13.28mgkg-1, and Cd was 0.53-0.59mgkg-1. Pb was found in the range of 5.22-7.99mgkg-1, Mn concentrations were in the range of 87.42-106.22mgkg-1, and the values for Fe were in the range of 167.49-230.47mgkg-1 while Cr and Ni levels were in the range of 16.82-25.99mgkg-1 and 2.65-4.67mgkg-1 respectively. Iron concentrations were highest in all the brands compared to the other metals; while the cadmium concentration was lowest in all the four brands cigarette analyzed. Generally the levels of content of the metals in all the brands except Zinc were high compared with the WHO threshold values. In addition to emphasizing the danger of cigarette smoking, the results highlighted the heavy metals toxicity potential of each brand of cigarett

Geochemical Partitioning of Major Elements in Brine Impacted Coal Fly Ash Residues

Fly ash-brine co-disposal technique has been considered as a way of disposing fly ash and brine (hyper-saline water) by some power stations in South Africa. This practice was aimed at using the fly ash to capture most of the elements in brine. However, the geochemical partitioning of the major elements in the waste materials after the fly ash-brine interaction has not been fully understood. This study focuses on understanding the geochemical partitioning of the major elements captured in the fly ash solid residues after the fly ash-brine interaction experiment. XRF and sequential extraction procedure were respectively applied to determine the chemical composition and partitioning of the major elements in fresh fly ash and the solid residues recovered after fly ash-brine interaction. The comparison of the results of the XRF analysis carried out on the fresh fly ash and the solid residues showed that the major elements such as Si, Ca, Mg and Na increased in the solid residues after the fly ash-brine interaction. This indicates that Ca, Mg and Na in the brine solution were captured by the fly ash during the interaction. However, the sequential extraction results showed that significant concentrations of Ca, Na and Mg were released into the water soluble, exchangeable and carbonate fractions. The results show that significant amounts of the elements captured in the fly ash solid residues during fly ash-brine interaction exist in the form which can be easily leached out when in contact with aqueous solution

Enhanced photovoltaic effects of microwave-assisted polyolsynthesized Cu2(Pd/Zn)SnS4 kesterite nanoparticles

Kesterite materials show excellent optical and semiconductive properties for use as petype absorber layer in photovoltaic (PV) applications, but they have a high open circuit voltage deficit (Voc,def) due to high antisite defect and secondary phase formation, resulting in poor device performance. This work reports a PV cell composed of Cu2PdSnS4 (CPTS) nanoparticles as an absorber layer yielding highly improved Voc of 900 mV, which is two times that of fabricated pristine Cu2ZnSnS4 (CZTS) PV cell. Improved PV cell parameters such as fillefactor (FF) of 83.4% and power conversion efficiency (PCE) of 1.01% were obtained for CPTS devices which are 3efold that of pristine CZTS devices. Optical studies revealed enhanced redshift absorption for CPTS nanoparticles. Electrochemical studies show improved current production, high electron mobility and low charge resistance for CPTS nanoparticles. This study shows that the improved photovoltaic properties can be attributed to enhancement in the bulk properties when Zn atoms are replaced by Pd atoms in kesterite nanomaterials as absorber layer material for PV applications

Alpha-glucosidase and alpha-amylase inhibitory activities, molecular docking, and antioxidant capacities of plectranthus ecklonii constituents

Shortage in insulin secretion or degradation of produced insulin is the principal characteristic of the metabolic disorder of diabetes mellitus (DM). However, because the current medications for the treatment of DM have many detrimental side effects, it is necessary to develop more effective antidiabetic drugs with minimal side effects. Alpha-glucosidase and alpha-amylase inhibitors are directly implicated in the delay of carbohydrate digestion. Pharmacologically, these inhibitors could be targeted for the reduction in glucose absorption rate and, subsequently, decreasing the postprandial rise in plasma glucose and the risk for long-term diabetes complications. The main objectives of this research study were to isolate different phytochemical constituents present in the methanolic extract of Plectranthus ecklonii and evaluate their alpha-glucosidase and alpha-amylase inhibitory activities and antioxidant capacity

Instrumental techniques for characterization of molybdenum disulphide nanostructures

The excellent chemical and physical properties of materials (nanomaterials) with dimensions of less than 100 nm (nanometers) resulted in researchers and industrialists to have great interest in their discovery and applications in various systems/applications. As their sizes are reduced to nanoscale, these nanomaterials tend to possess exceptional properties differing from those of their bulk counterparts; hence, they have found applications in electronics and medicines. In order to apply them in those applications, there is a need to synthesise these nanomaterials and study their structural, optical, and electrochemical properties. Among several nanomaterials, molybdenum disulphide (MoS2) has received a great interest in energy applications due to its exceptional properties such as stability, conductivity, and catalytic activities. Hence, the great challenge lies in finding the state-of-the-art characterization techniques to reveal the different properties of MoS2 nanostructures with great accuracy. In this regard, there is a need to study and employ several techniques to accurately study the surface chemistry and physics of the MoS2 nanostructures. Hence, this review will comprehensively discuss a detailed literature survey on analytical techniques that can be used to study the chemical, physical, and surface properties of MoS2 nanostructures, namely, ultraviolet-visible spectroscopy (UV-vis), photoluminescence spectroscopy (PL), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, time-of-flight secondary ion mass spectroscopy (TOF-SIMS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning and transmission electron microscopies (SEM and TEM), atomic force microscopy (AFM), energy dispersive X-ray spectroscopy (EDS/X), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and electroanalytical methods which include linear sweep (LSV) and cyclic (CV) voltammetry and electrochemical impedance spectroscopy (EIS)

Spectroelectrochemical reactivities of novel polyaniline nanotube pesticide biosensors

Summary: The preparation and characterisation of electrosynthetic polyaniline nanomaterials doped with phenanthrene sulphonic acid (PSA) is being presented. The polymeric nanomaterials prepared include processable poly(o-methoxy aniline) (POMA) and poly(2,5-dimethoxy aniline) (PDMA). Spectroelectrochemical reactivities of the electroactive polymeric nanotube systems as well as the nanobiosensor systems were studied by SEM, FTIR, UV-Vis and Subtractively Normalised Fourier Transformed Infrared Spectroscopy (SNIFTIRS) techniques. Furthermore, cyclic and differential pulse voltammetric studies of the nanomaterials were also performed using platinum or thiol-modulated gold electrodes. The SEM studies confirmed the nanorod morphology of the polyanilines. The heterogeneous rate constant, k o , for the nanopolymeric material and the diffusion coefficient of electrons, D e , was calculated and found to be in agreement with values expected for electron hopping along conducting polymer chains. Organophosphate pesticide nanobiosensor devices were prepared by encapsulating acetylcholinesterase (AChE) in the nanopolymeric composite. The biosensor amperometric response to the organophosphate pesticide called diazinon and the carbamate pesticide called carbofuran were studied. The sensor responses to pesticides followed typical electrochemical Michaelis-Menten kinetics

Laboratory study on the mobility of major species in fly ash–brine co-disposal systems: up-flow percolation test

Apart from the generation of fly ash, brine (hyper-saline wastewater) is also a waste material generated in South African power stations as a result of water re-use. These waste materials contain major species such as Al, Si, Na, K, Ca, Mg, Cl and SO4. The co-disposal of fly ash and brine has been practiced by some power stations in South Africa with the aim of utilizing the fly ash to capture the salts in brine. The effect of the chemical interaction of the species contained in both fly ash and brine, when co-disposed, on the mobility of species in the fly ash–brine systems is the focus of this study. The up-flow percolation test was employed to determine the mobility of some major species in the fly ash–brine systems. The results of the analysed eluates from the up-flow percolation tests revealed that some species such as Al, Ca and Na were leached from the fly ash into the brine solution while some species such as Mg, Cl and SO4 were removed to some extent from the brine solution during the interaction with fly ash. The pH of the up-flow percolation systems was observed to play a significant role on the mobility of major species from the fly ash–brine systems. The study showed that some major species such as Mg, Cl and SO4 could be removed from brine solution using fly ash when certain amount of brine percolates through the ash.Web of Scienc