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Publikacije (9)

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V. Stanković, Sladana Durdic, M. Ognjanović, G. Zlatić, D. Stanković

In this study, we propose an eco-friendly method for synthesizing cerium tungstate nanoparticles using hydrothermal techniques. We used scanning, transmission electron microscopy, and X-ray diffraction to analyze the morphology of the synthesized nanoparticles. The results showed that the synthesized nanoparticles were uniform and highly crystalline, with a particle size of about 50 nm. The electrocatalytic properties of the nanoparticles were then investigated using cyclic voltammetry and electrochemical impedance spectroscopy. We further used the synthesized nanoparticles to develop an electrochemical sensor based on a carbon paste electrode that can detect hydroquinone. By optimizing the differential pulse voltammetric method, a wide linearity range of 0.4 to 45 µM and a low detection limit of 0.06 µM were obtained. The developed sensor also expressed excellent repeatability (RSD up to 3.8%) and reproducibility (RSD below 5%). Interferences had an insignificant impact on the determination of analytes, making it possible to use this method for monitoring hydroquinone concentrations in tap water. This study introduces a new approach to the chemistry of materials and the environment and demonstrates that a careful selection of components can lead to new horizons in analytical chemistry.

Ivana Martinović, G. Zlatić, Z. Pilić, M. Šušak, F. Falak

The cyclic voltammogram recorded in the potential range between 0 V and 800 mV with scan rate of 100 mV s −1 was used to determine the measure of antioxidants content (antioxidant capacity) present in Sambucus nigra L. extract. The antioxidant capacity of the extract was 4.06 mg GAE g −1 fw (mg of gallic acid equivalents per gram of fresh weight of the extract). The corrosion inhibition efficiency of Sambucus nigra L. extract on aluminium, copper, and bronze in 3 % NaCl solution was studied by potentiodynamic polarization and electrochemical impedance spectroscopy. Polarization data showed that extract acted as a mixed-type inhibitor, that the corrosion inhibition process was spontaneous physical adsorption (Δ G ≈ –16 kJ mol –1 ) of the extract molecules on metals surfaces and followed Freundlich isotherm. Impedance spectroscopy studies revealed that increasing the concentration of extract reduced the double-layer capacitance and increased the charge transfer resistance. The highest inhibition efficiencies (Cu: ~ 57 %, CuSn14: ~74 % and Al: ~58 %) were achieved for an extract concentration of 1.0 g L –1 .

G. Zlatić, Ivana Martinović, Z. Pilić, Andrea Paut, Ivana Mitar, A. Prkić, Dušan Čulum

Plant extracts are increasingly being examined in the corrosion inhibition of metal and alloys in various environments due to their potent antioxidant properties. The use of Artemisia annua L. aqueous extract (AAE) as an aluminium alloy 5083 (ALA) corrosion inhibitor in artificial seawater (ASW) was investigated using electrochemical tests and spectroscopy tools, while the active biocompounds found in AAE were analyzed using high-performance liquid chromatography (HPLC). Electrochemical results showed that AAE acts as an anodic inhibitor through the physisorption (ΔG ≈ –16.33 kJ mol−1) of extract molecules on the ALA surface, thus reducing the active sites for the dissolution of the alloy in ASW. Fourier-transform infrared spectra confirmed that phenolic acids found in AAE formed the surface layer that protects ALA against the corrosive marine environment, while HPLC analysis confirmed that the main phytoconstituents of AAE were chlorogenic acid and caffeic acid. The inhibition action of phenolic acids and their derivatives found in the AAE was based on the physisorption of caffeic acid on the ALA surface, which improved physicochemical properties of the barrier film and/or conversion of Al3+ to elemental aluminium by phenolic acids as reducens, which slowed down the diffusion rate of Al3+ to or from the ALA surfaces. The protective effect of the surface layer formed in the presence of AAE against ASW was also confirmed by inductively coupled plasma–optical emission spectrometry (ICP-OES) whereby the measured concentration of Al ions after 1 h of immersion of ALA in the pure ASW was 15.30 μg L−1 cm−2, while after the addition of 1 g L−1 AAE, the concentration was 3.09 μg L−1 cm−2.

G. Zlatić, Anamarija Arapović, Ivana Martinović, Anita Martinović Bevanda, P. Bošković, A. Prkić, Andrea Paut, Tina Vukusic

Considering the vast cultural and traditional heritage of the use of aromatic herbs and wildflowers for the treatment of light medical conditions in the Balkans, a comparison of the antioxidant capacity of wildflowers extracts from Herzegovina was studied using both cyclic voltammetry and spectrophotometry. The cyclic voltammograms taken in the potential range between 0 V and 800 mV and scan rate of 100 mV s−1 were used for the quantification of the electrochemical properties of polyphenols present in four aqueous plant extracts. Antioxidant capacity expressed as mmoL of gallic acid equivalents per gram of dried weight of the sample (mmoL GAE g−1 dw) was deduced from the area below the major anodic peaks (Q400 pH 6.0, Q500 pH 4.7, Q600 pH 3.6). The results of electrochemical measurements suggest that the major contributors of antioxidant properties of examined plants are polyphenolic compounds that contain ortho-dihydroxy-phenol or gallate groups. Using Ferric reducing-antioxidant power (FRAP) and 2,2′-azino-bis spectrophotometric methods (3-ethylbenzthiazoline-6-sulphonic acid) radical cation-scavenging activity (ABTS) additionally determined antioxidant capacity. The FRAP results ranged from 2.9702–9.9418 mmoL Fe/g dw, while the results for ABTS assays expressed as Trolox equivalents (TE) ranged from 14.1842–42.6217 mmoL TE/g dw. The Folin–Ciocalteu procedure was applied to determine the total phenolics content (TP). The TP content expressed as Gallic acid equivalents (GAE) ranged from 6.0343–9.472 mmoL GAE/g dw. The measurements of total flavonoid (TF) and total condensed tannin (TT) contents were also performed to obtain a broader polyphenolic profile of tested plant materials. Origanum vulgare L. scored the highest on each test, with the exception of TT content, followed by the Mentha × piperita L., Artemisia annua L., and Artemisia absinthium L., respectively. The highest TT content, expressed as mg of (−)catechin equivalents per gram of dried weight of sample (mg CE/g dw), was achieved with A. absinthium extract (119.230 mg CE/g dw) followed by O. vulgare (90.384 mg CE/g dw), A. annua (86.538 mg CE/g dw) and M. piperita (69.231 mg CE/g dw), respectively. In addition, a very good correlation between electrochemical and spectroscopic methods was achieved.

Ivana Martinović, Z. Pilić, G. Zlatić, M. Barišić, S. Čelan

Extract of Alchemilla vulgaris L. was investigated as eco-friendly corrosion inhibitor for aluminium in 3 % NaCl using electrochemical techniques. According to the results, inhibition efficiency increases with the increase concentration of extract and the highest efficiency (~80 %) is recorded for the maximal concentration of extract (1.0 g L–1). The inhibition activity of extract occurs by the spontaneous physisorption (ΔG ≈ –16 kJ mol–1) on active sites of aluminium surface that follows Freundlich isotherm. Polarization curves showed that Alchemilla vulgaris L. extract act s a mixed-type inhibitor. The effect of temperature on the aluminium corrosion and inhibition action of extract was studied and the result showed that the corrosion rate increased and the inhibitor efficiency decreased with increase of temperature. The calculated values of the activation energy confirmed presence of inhibitive Alchemilla vulgaris L. extract on aluminium surface.

Ivana Martinović, G. Zlatić, Z. Pilić, Lucija Šušić, Olga Kowalska, Dan Petrovic, F. Falak, J. Mišković

The adsorption and corrosion inhibition of alkanethiols self-assembled monolayer on the copper surface in simulated acid rain were investigated by electrochemical techniques. Self-assembled monolayer (SAM) was formed by 1-octanethiol (OT), 1-dodecanethiol (DT) and 1-octadecanethiol (ODT) molecules on copper surface. The experimental results showed that inhibiton efficiency increases simultaneously with increase of concentration and chain length of thiols. At the concentration of 0.5 mmol L ─1 , 1-octadecanethiol (ODT) acts as effective corrosion inhibitor with inhibition efficiency of ~ 90%. The adsorption of alkanethiol self-assembled monolayer on the copper surface was investigated by polarization measurements. The adsorption of SAMs on the copper surface followed Langmuir isotherm and the standard Gibbs energy indicated that the adsorption mechanism of OT, DT and ODT on copper is the hybrid type of physical and chemical adsorption. Values of Gibbs energy ranging from ─24 kJ mol ─1 for OT to ─32 kJ mol ─1 for ODT indicate that the chemisorption part in the adsorption mechanism prevails with the increase of alkanethiols chain length.

Z. Pilić, Ivana Martinović, Marija Pavlinović, G. Zlatić

The aqueous extract of the Helichrysum italicum leaves (HI) is tested as a corrosion inhibitor of an iron in a simulated acid rain using potentiodynamic polarisation, cyclic voltammetry and electrochemical impedance spectroscopy. Results of all electrochemical methods indicate an increase of a corrosion inhibition efficiency of the iron with the HI extract concentration. Maximum inhibition efficiency (~ 50 %) is obtained at 2.0 g L–1 HI extract. The inhibitive action is assumed to occur via an adsorption of the HI extract on the iron surface. Results indicate that the adsorption process is spontaneous and follows the Freundlich adsorption isotherm. According to the calculated ΔG value (~ 15 kJ mol–1), the corrosion inhibition of the iron occurs predominantly via a physisorption of the HI extract. The concentration of iron ions released into a solution, measured by atomic absorption spectrometry, is in accordance with the electrochemical results.

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