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111.
Biotransformation of copper oxide nanoparticles by the pathogenic fungus Botrytis cinerea
Eva Kovačec, Marjana Regvar, Johannes Teun van Elteren, Iztok Arčon, Tamás Papp, Darko Makovec, Katarina Vogel-Mikuš, 2017, original scientific article

Abstract: Two plant pathogenic fungi, Botrytis cinerea and Alternaria alternata, isolated from crop plants, were exposed to Cu in ionic (Cu2þ), microparticulate (MP, CuO) or nanoparticulate (NP, Cu or CuO) form, in solid and liquid culturing media in order to test fungal response and toxic effects of the mentioned compounds for the potential use as fungicides. B. cinerea has shown pronounced growth and lower levels of lipid peroxidation compared to A. alternata. Its higher resistance/tolerance is attributed mainly to biotransformation of CuO and Cu NPs and CuO MPs into a blue compound at the fungal/culturing media interface, recognized by Cu K-edge EXAFS analysis as Cu-oxalate complex. The pronounced activity of catechol-type siderophores and organic acid secretion in B. cinerea induce leaching and mobilization of Cu ions from the particles and their further complexation with extracellularly secreted oxalic acid. The ability of pathogenic fungus to biotransform CuO MPs and NPs hampers their use as fungicides. However the results show that B. cinerea has a potential to be used in degradation of Cu(O) nanoparticles in environment, copper extraction and purification techniques.
Keywords: copper, metal oxide nanoparticles, detoxification mechanisms, metal pollution, Cu-oxalate
Published in RUNG: 23.08.2017; Views: 4267; Downloads: 0
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112.
Edge profiles in K shell photoabsorption spectra of gaseous hydrides of 3p elements and homologues
Robert Hauko, Jana Padežnik Gomilšek, Alojz Kodre, Iztok Arčon, Giuliana Aquilanti, original scientific article

Abstract: Photoabsorption spectra of gaseous hydrides of 3p elements (PH3, H2S, HCl) are measured in the energy region of photoexcitations pertaining to K edge. The analysis of the edge profile is extended to hydrides of 4p series (GeH4, AsH3, H2Se, HBr) from an earlier experiment, and to published spectra of 2p hydrides (CH4, NH3, H2O, HF) and noble gases Ar, Kr and Ne and SiH4. The edge profiles are modelled with a linear combination of lorentzian components, describing excitations to individual bound states and to continuum. Transition energies and probabilities are also calculated in the non-relativistic molecular model of the ORCA code, in good agreement with the experiment. Edge profiles in the heavier homologues are closely similar, the symmetry of the molecule governs the transitions to the lowest unoccupied orbitals. In 2p series the effect of the strong nuclear potential prevails. Transitions to higher, atomic-like levels remain very much the same as in free atoms.
Keywords: X-ray absorption spectra, gaseous hydrides, 3p K-edge spectra, DFT
Published in RUNG: 23.08.2017; Views: 3570; Downloads: 0
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113.
Electrochemical dissolution of iridium and iridium oxide particles in acidic media : transmission electron microscopy, electrochemical flow cell coupled to inductively coupled plasma mass spectrometry and X-ray absorption spectroscopy study
Primož Jovanovič, Nejc Hodnik, Francisco Ruiz-Zepeda, Iztok Arčon, Barbara Jozinović, Milena Zorko, Marjan Bele, Martin Šala, Vid Simon Šelih, Samo B. Hočevar, Miran Gaberšček, 2017, original scientific article

Abstract: Iridium based particles as the most promising proton exchange membrane electrolyser electrocatalysts were investigated by transmission electron microscopy (TEM), and by coupling of electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometer (ICP-MS). Additionally, a thin-film rotating disc electrode (RDE), an identical location transmission and scanning electron microscopy (IL-TEM and IL-SEM) as well as an X-ray absorption spectroscopy (XAS) studies have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that iridium particles dissolved already well below oxygen evolution reaction (OER) potentials, presumably induced by iridium surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile type IrO2 particles (T-IrO2) are substantially more stable and less active in comparison to as prepared metallic (A-Ir) and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER relevant conditions E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyser.
Keywords: Iridium Oxide Par-ticles, Electrochemical Dissolution of Iridium, Ir L3-edge XANES
Published in RUNG: 23.08.2017; Views: 3786; Downloads: 0
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114.
115.
Correlations between photocatalytic activity and Cu structure in Cu-modified TiO2-SiO2
T. Čižmar, published scientific conference contribution abstract

Keywords: Titanium dioxide, Cu-modified, TiO2-SiO2, photocatalysts, photocatalytic activity, Cu K-edge XANES, EXAFS
Published in RUNG: 26.06.2017; Views: 4504; Downloads: 0
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116.
An extracellular polymeric substance quickly chelates mercury(II) with N-heterocyclic groups
Franco Baldi, Michele Gallo, Salvatore Daniale, Dario Battistel, Claudia Faleri, Alojz Kodre, Iztok Arčon, 2017, original scientific article

Abstract: A strain of Klebsiella oxytoca DSM 29614 is grown on sodium citrate in the presence of 50 mg l−1 of Hg as Hg(NO3)2. During growth, the strain produces an extracellular polymeric substance (EPS), constituted by a mixture of proteins and a specific exopolysaccharide. The protein components, derived from the outer membrane of cells, are co-extracted with the extracellular exopolysaccharide using ethanol. The extracted EPS contains 7.5% of Hg (total amount). This indicates that EPS is an excellent material for the biosorption of Hg2+, through chemical complexation with the EPS components. The binding capacity of these species towards Hg2+ is studied by cyclic voltammetry, and Hg L3-edge XANES and EXAFS spectroscopy. The results found indicate that Hg2+ is mainly bound to the nitrogen of the imidazole ring or other N-heterocycle compounds. The hydroxyl moities of sugars and/or the carboxyl groups of two glucuronic acids in the polysaccharide can also play an important role in sequestring Hg2+ ions. However, N-heterocyclic groups of proteins bind Hg2+ faster than hydroxyl and carboxyl groups of the polysaccharide.
Keywords: Klebsiella oxytoca, Biosorption, Proteins, Polysaccharide, Cyclic voltammetry, EXAFS analysis
Published in RUNG: 03.03.2017; Views: 4562; Downloads: 0
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117.
The mechanism of Li2S activation in lithium-sulfur batteries: Can we avoid the polysulfide formation?
Alen Vižintin, Laurent Chabanne, Elena Tchernychova, Iztok Arčon, Lorenzo Stievano, Giuliana Aquilanti, Markus Antonietti, Tim-Patric Fellinger, Robert Dominko, 2017, original scientific article

Abstract: Electrochemical reactions in the LieS batteries are considered as a multistep reaction process with at least 2e3 equilibrium states. Here we report a possibility of having a conversion of Li2S into sulfur without detectible formation of polysulfides. That was confirmed by using a novel material system consisting of carbon coated Li2S particles prepared by carbothermal reduction of Li2SO4. Two independent in operando measurements showed direct oxidation of Li2S into sulfur for this system, with almost negligible formation of polysulfides at potentials above 2.5 V vs. Li/Liþ. Our results link the diversity of first charge profiles in the literature to the Li2S oxidation mechanism and show the importance of ionic wiring within the material. Furthermore, we demonstrate that the Li2S oxidation mechanism depends on the relative amount of soluble sulfur in the electrolyte. By controlling the type and the amount of electrolyte within the encapsulating carbon shell, it is thereby possible to control the reaction mechanism of Li2S activation.
Keywords: Lithium-sulfur batteries Li2S active material XAS UV/Vis spectroscopy Li2S activation
Published in RUNG: 03.03.2017; Views: 5058; Downloads: 0
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118.
Operando characterization of batteries using x-ray absorption spectroscopy: advances at the beamline XAFS at synchrotron Elettra
Giuliana Aquilanti, marco Giorgetti, Robert Dominko, Lorenzo Stievano, Iztok Arčon, Nicola Novello, Luca Ivanc Olivieri, 2017, original scientific article

Abstract: X-ray absorption spectroscopy is a synchrotron radiation based technique that is able to provide information on both local structure and electronic properties in a chemically selective manner. It can be used to characterize the dynamic processes that govern the electrochemical energy storage in batteries, and to shed light on the redox chemistry and changes in structure during galvanostatic cycling to design cathode materials with improved properties. Operando XAS studies have been performed at beamline XAFS at Elettra on different systems. For Li-ion batteries, a multiedge approach revealed the role of the different cathode components during the charge and discharge of the battery. In addition, Li-S batteries for automotive applications were studied. Operando sulfur K-edge XANES and EXAFS analysis was used to characterize the redox chemistry of sulfur, and to relate the electrochemical mechanism to its local structure.
Keywords: operando studies, x-ray absorption spectroscopy, Li-ion batteries, Li-S batteries
Published in RUNG: 03.03.2017; Views: 6075; Downloads: 0
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119.
Correlations between photocatalytic activity and chemical structure of Cu-modified TiO [sub] 2-SiO [sub] 2 nanoparticle composites
T. Čižmar, Iztok Arčon, Urška Lavrenčič Štangar, 2016, published scientific conference contribution abstract

Keywords: Cu-modified TiO2-SiO2, sol-gel, XANES, EXAFS
Published in RUNG: 06.02.2017; Views: 4125; Downloads: 0
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120.
Correlations between photocatalytic activity and chemical structure of Cu-modified TiO2–SiO2 nanoparticle composites
T. Čižmar, Urška Lavrenčič Štangar, Iztok Arčon, 2016, original scientific article

Abstract: Copper-modified TiO2–SiO2photocatalysts were prepared by sol–gel method based on organic copper,silicon and titanium precursors. Copper concentration varied from 0.1 to 3.0 mol%. A widely appliedmodel reaction of photocatalytic oxidation of terephtalic acid (TPA) in water solution was used in order toevaluate the catalytic activities of elaborated samples. The crystal structures of the titania components ofall tested titania–silica species were studied using XRD analysis. The influence of Cu2+cation incorporationon the crystal structure of titania, as well as the chemical states and the neighbouring structures of coppercations, have been examined by means of Cu K-edge EXAFS and XANES analysis. The experimental datashow that there is a ten times increase in photocatalytic activity when TiO2–SiO2matrix is modified with0.1 mol% of Cu. It can be supposed that an enhancement of photocatalytic activity of low-concentratedcopper-modified titania–silica nanocomposites is probably due to a close attachment of Cu2+cationsto the surfaces of photocatalytically active TiO2nanoparticles. In this case, Cu2+cations may possiblyact as free electron traps reducing the intensity of recombination between opposite free charge carriers(electrons, holes) available at the photocatalyst’s surface.
Keywords: Cu-modified TiO2–SiO2photocatalysts, Titanium dioxide, Metal doping, Cu K-edge XANES, EXAFS, Photocatalytic activitya
Published in RUNG: 17.01.2017; Views: 5135; Downloads: 0
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