Dragan Manojlović

Assessment of heavy metal pollutants accumulation in the Tisza river sediments.

In this study we have worked on the evaluation of heavy metal contamination in the sediments taken from the Tisza River and its tributaries, and thereby used the sequential extraction method, geochemical normalization, the calculation of the enrichment factor (EF), and the methods of statistical analysis. The chemical fractionation of Ni, Cu, Zn, Cr, Pb, Fe, and Mn, carried out by using the modified Tessier method, points to different substrates and binding mechanisms of Cu, Zn and Pb in sediments of the tributaries and sediments of the Tisza River. The similarities in the distributions of Fe and Ni in all types of sediments are the result of geochemical similarity as well as of the fact that natural sources mainly affect the concentration levels of these elements. The calculated enrichment factors (EF, measured metal vs. background concentrations) indicated that metal contamination (Cu, Pb, Zn and Cr) was recorded in the sediments of the Tisza River, while no indications of pollution were detected in the tributaries of the Tisza River and the surrounding pools. The maximum values of the EF were close to 6 for Cu and Pb (moderately severe enrichment) and close to 4.5 for Zn (indicating moderate enrichment). It can be said that the Tisza River is slightly to moderately severely polluted with Cu, Zn, and Pb, and minorly polluted with Cr. It is concluded that sediments of the Tisza serve as a repository for heavy metal accumulation from adjacent urban and industrial areas.

Electrochemical Behavior and Antioxidant and Prooxidant Activity of Natural Phenolics

We have investigated the electrochemical oxidation of a number natural phenolics (salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, protocatechuic acid, o-coumaric acid, m-coumaric acid, p-coumaric acid, caffeic acid, quercetin and rutin) using cyclic voltammetry. The antioxidant properties of these compounds were also studied. A structural analysis of the tested phenolics suggests that multiple OH substitution and conjugation are important determinants of the free radical scavenging activity and electrochemical behavior. Compounds with low oxidation potentials (Epa lower than 0.45) showed antioxidant activity, whereas compounds with high Epa values (>0.45) act as prooxidants.

Decolorization of reactive textile dyes using water falling film dielectric barrier discharge

Decolorization of reactive textile dyes Reactive Black 5, Reactive Blue 52, Reactive Yellow 125 and Reactive Green 15 was studied using advanced oxidation processes (AOPs) in a non-thermal plasma reactor, based on coaxial water falling film dielectric barrier discharge (DBD). Used initial dye concentrations in the solution were 40.0 and 80.0mg/L. The effects of different initial pH of dye solutions, and addition of homogeneous catalysts (H(2)O(2), Fe(2+) and Cu(2+)) on the decolorization during subsequent recirculation of dye solution through the DBD reactor, i.e. applied energy density (45-315kJ/L) were studied. Influence of residence time was investigated over a period of 24h. Change of pH values and effect of pH adjustments of dye solution after each recirculation on the decolorization was also tested. It was found that the initial pH of dye solutions and pH adjustments of dye solution after each recirculation did not influence the decolorization. The most effective decolorization of 97% was obtained with addition of 10mM H(2)O(2) in a system of 80.0mg/L Reactive Black 5 with applied energy density of 45kJ/L, after residence time of 24h from plasma treatment. Toxicity was evaluated using the brine shrimp Artemia salina as a test organism.

Light-Emitting Electrochemical “Swimmers”†

Swimmer in the dark: propulsion of a conducting object is intrinsically coupled with light emission using bipolar electrochemistry. Asymmetric redox activity on the surface of the swimmer (black bead) causes production of gas bubbles to propel the swimmer in a glass tube with simultaneous electrochemiluminescence (ECL) emission to monitor the progress of the swimmer.

Synthesis, characterization, electrochemical studies and antitumor activity of some new chalcone analogues containing ferrocenyl pyrazole moiety

A series of new alpha,beta-unsaturated conjugated ketones containing ferrocenyl pyrazole unit were synthesized and fully characterized by IR and NMR spectroscopy. Electrochemical characterization of subject compounds was performed by means of cyclic voltametry. The in vitro cytotoxic activity of all the synthesized compounds was studied against cervix adenocarcinoma HeLa, melanoma Fem-x and myelogenous leukemia K562 cell lines by the MTT method. Derivative 1l containing 3-pyridyl moiety exhibited a better cytotoxic activity in the cell growth inhibition of K562 cell lines in comparison with cisplatin as a reference compound.

Degradation of triketone herbicides, mesotrione and sulcotrione, using advanced oxidation processes

Degradation of two triketone herbicides, mesotrione and sulcotrione, was studied using four different advanced oxidation processes (AOPs): ozonization, dielectric barrier discharge (DBD reactor), photocatalysis and Fenton reagent, in order to find differences in mechanism of degradation. Degradation products were identified by high performance liquid chromatography (HPLC-DAD) and UHPLC-Orbitrap-MS analyses. A simple mechanism of degradation for different AOP was proposed. Thirteen products were identified during all degradations for both pesticides. It was assumed that the oxidation mechanisms in the all four technologies were not based only on the production and use of the hydroxyl radical, but they also included other kinds of oxidation mechanisms specific for each technology. Similarity was observed between degradation mechanism of ozonation and DBD. The greatest difference in the products was found in Fenton degradation which included the opening of benzene ring. When degraded with same AOP pesticides gave at the end of treatment the same products. Global toxicity and COD value of samples was determined after all degradations. Real water sample was used to study influence of organic matter on pesticide degradation. These results could lead to accurate estimates of the overall effects of triketone herbicides on environmental ecosystems and also contributed to the development of improved removal processes.

A Sensitive Electrochemiluminescence Immunosensor for Celiac Disease Diagnosis Based on Nanoelectrode Ensembles

We report here the design of a novel immunosensor and its application for celiac disease diagnosis, based on an electrogenerated chemiluminescence (ECL) readout, using membrane-templated gold nanoelectrode ensembles (NEEs) as a detection platform. An original sensing strategy is presented by segregating spatially the initial electrochemical reaction and the location of the immobilized biomolecules where ECL is finally emitted. The recognition scaffold is the following: tissue transglutaminase (tTG) is immobilized as a capturing agent on the polycarbonate (PC) surface of the track-etched templating membrane. It captures the target tissue transglutaminase antibody (anti-tTG), and finally allows the immobilization of a streptavidin-modified ruthenium-based ECL label via reaction with a suitable biotinylated secondary antibody. The application of an oxidizing potential in a tri-n-propylamine (TPrA) solution generates an intense and sharp ECL signal, suitable for analytical purposes. Voltammetric and ECL analyses evidenced that the ruthenium complex is not oxidized directly at the surface of the nanoelectrodes; instead ECL is generated following the TPrA oxidation, which produces the TPrA•+ and TPrA• radicals. With NEEs operating under total overlap diffusion conditions, high local fluxes of these reactive radicals are produced by the nanoelectrodes in the immediate vicinity of the ECL labels, so that they efficiently generate the ECL signal. The radicals can diffuse over short distances and react with the Ru(bpy)32+ label. In addition, the ECL emission is obtained by applying a potential of 0.88 V versus Ag/AgCl, which is about 0.3 V lower than when ECL is initiated by the electrochemical oxidation of Ru(bpy)3(2+). The immunosensor provides ECL signals which scale with anti-tTG concentration with a linearity range between 1.5 ng·mL–1 and 10 μg·mL–1 and a detection limit of 0.5 ng·mL–1. The sensor is finally applied to the analysis of anti-tTG in human serum samples, showing to be suitable to discriminate between healthy and celiac patients.

Mapping electrogenerated chemiluminescence reactivity in space: mechanistic insight into model systems used in immunoassays

The remarkable characteristics of electrogenerated chemiluminescence (ECL) as a readout method are successfully exploited in numerous microbead-based immunoassays. However there is still a lack of understanding of the extremely high sensitivity of such ECL bioassays. Here the mechanisms of the reaction of the Ru(bpy)32+ luminophore with two efficient co-reactants (TPrA or DBAE) were investigated by mapping the ECL reactivity at the level of single Ru(bpy)32+-functionalized beads. Micrometric non-conductive beads were decorated with the ruthenium label via a sandwich immunoassay or via a peptide bond. Mapping the ECL reactivity on one bead demonstrates the generation of the excited state at a micrometric distance from the electrode by reaction of surface-confined Ru(bpy)32+ with diffusing TPrA radicals. The signature of the TPA˙+ lifetime is obtained from the ECL profile. Unlike the reaction with Ru(bpy)32+ in solution, DBAE generates very low ECL intensity in the bead-based format suggesting more unstable radical intermediates. The 3D imaging approach provides insights into the ECL mechanistic route operating in bioassays and on the optical effects that focus the ECL emission.

Magnetization enhancement in nanostructured random type MgFe2O4 spinel prepared by soft mechanochemical route

In this paper we report results of structural, spectroscopic, and magnetic investigations of MgFe2O4 nanoparticles prepared by soft mechanochemical synthesis. MgFe2O4 nanoparticles crystallize in Fd3¯m space group with mixed cation distribution and reduced percentage of Fe3+ at tetrahedral (8a) sites. Discrepancy in the cation distribution compared to that in the bulk Mg–ferrite is one of the highest known. X-ray line broadening analysis reveals crystallite size and strain anisotropy. The saturation magnetization, Msat=62 emu/g measured at 5 K is twice higher than that found in the bulk counterparts. Such high value of Msat is attributed to the low value of cation inversion parameter (δ=0.69), to the core/shell structure of the nanoparticles and to the surface/volume ratio. Mossbauer spectrum collected at room temperature reveals ferrimagnetic ordering between Fe3+ ions in 8a and 16d sites, while zero-field-cooled (ZFC) and field-cooled (FC) M(T) measurements were shown superparamagnetic state above 350 K.

Application of non-thermal plasma reactor and Fenton reaction for degradation of ibuprofen.

Pharmaceutical compounds have been detected frequently in surface and ground water. Advanced Oxidation Processes (AOPs) were reported as very efficient for removal of various organic compounds. Nevertheless, due to incomplete degradation, toxic intermediates can induce more severe effects than the parent compound. Therefore, toxicity studies are necessary for the evaluation of possible uses of AOPs. In this study the effectiveness and capacity for environmental application of three different AOPs were estimated. They were applied and evaluated for removal of ibuprofen from water solutions. Therefore, two treatments were performed in a non-thermal plasma reactor with dielectric barrier discharge with and without a homogenous catalyst (Fe(2+)). The third treatment was the Fenton reaction. The degradation rate of ibuprofen was measured by HPLC-DAD and the main degradation products were identified using LC-MS TOF. Twelve degradation products were identified, and there were differences according to the various treatments applied. Toxicity effects were determined with two bioassays: Vibrio fischeri and Artemia salina. The efficiency of AOPs was demonstrated for all treatments, where after 15 min degradation percentage was over 80% accompanied by opening of the aromatic ring. In the treatment with homogenous catalyst degradation reached 99%. V. fischeri toxicity test has shown greater sensitivity to ibuprofen solution after the Fenton treatment in comparison to A. salina.