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44. An extracellular polymeric substance quickly chelates mercury(II) with N-heterocyclic groupsFranco Baldi, Michele Gallo, Salvatore Daniale, Dario Battistel, Claudia Faleri, Alojz Kodre, Iztok Arčon, 2017, izvirni znanstveni članek Opis: 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.
Ključne besede: Klebsiella oxytoca, Biosorption, Proteins, Polysaccharide, Cyclic voltammetry, EXAFS analysis
Objavljeno v RUNG: 03.03.2017; Ogledov: 6295; Prenosov: 0
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46. Correlations between photocatalytic activity and chemical structure of Cu-modified TiO2–SiO2 nanoparticle compositesT. Čižmar, Urška Lavrenčič Štangar, Iztok Arčon, 2016, izvirni znanstveni članek Opis: 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.
Ključne besede: Cu-modified TiO2–SiO2photocatalysts, Titanium dioxide, Metal doping, Cu K-edge XANES, EXAFS, Photocatalytic activitya
Objavljeno v RUNG: 17.01.2017; Ogledov: 6727; Prenosov: 0
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47. Arbuscular mycorrhizal fungi alter Hg root uptake and ligand environment as studied by X-ray absorption fine structureAlojz Kodre, Iztok Arčon, Marta Debeljak, Mateja Potisek, Matevž Likar, Katarina Vogel-Mikuš, 2017, izvirni znanstveni članek Opis: Mercury (Hg) – plant – fungal interactions are only poorly studied. Hg speciation and ligand environment
in maize roots inoculated with arbuscular mycorrhizal (AM) fungi were investigated in order to better
understand the role of AM in Hg soil to root transfer.
The maize plants were grown in Hg polluted substrate (50 mg g1 as dissolved HgCl2) and inoculated
with AM fungi originating from: a) highly Hg polluted environment of a former Hg smelting site in Idrija,
Slovenia, (Glomus sp. – sample AmI), and b) non-polluted environment (commercial AM inoculum
Symbivit1 – sample AmC). Hg speciation and ligand environment in maize roots was studied by Hg-L3
XANES and EXAFS with emphasis on XAS methodology – modelling and fitting the XAFS spectra to extract in a reliable way as much information on Hg coordination as possible. The AmI plants developed more arbuscules and less vesicles than the AmC plants, and also
accumulated more Hg in the roots. A clear difference in Hg coordination between the AM (AmC & AmI)
and the control (ConC & ConI) plants is recognized in Hg L3-edge EXAFS analysis: in the ConC & ConI
maize roots 73–80% of Hg is attached between two sulphur atoms at the distance of 2.34 Å. The remaining
ligand is nitrogen at 2.04 Å. In AmI & AmC roots another Hg-S attachment encompassing four thiol groups
at the S-distance of 2.50 Å are identified, accounting for 21–26%. AM fungi can modify Hg ligand environment in plant roots, thus playing an important role in biogeochemical cycling of Hg in terrestrial
ecosystems.
Ključne besede: EXAFS
XANES
Arbuscular mycorrhiza
Phytoremediation
Toxicity
Hg coordination
Ligand environment
Objavljeno v RUNG: 27.09.2016; Ogledov: 8000; Prenosov: 0
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48. XAS and micro-XRF analysis of mono and bi-metallic exopolysaccharide (FePd-EPS) bio-generated by K. oxytocaIztok Arčon, Stefano Paganelli, Oreste Piccolo, Michele Gallo, Katarina Vogel-Mikuš, Franco Baldi, 2016, objavljeni povzetek znanstvenega prispevka na konferenci Opis: Bacteria Klebsiella oxytoca (DSM 29614) secret a specific exopolysaccharide (EPS) in the presence of Fe(III)-citrate, as sole carbon and energy source, and produces after 7 days an iron gel precipitate (Fe-EPS) [1]. In the presence of palladium or other metal species, the culture of K. oxytoca can produce other mono or bimetal species (Pd-EPS, FePd-EPS) [2]. These bio-materials may be used as green biogenerated catalysts or for other biotechnological purposes. In this work we present the analysis of the morphology and the chemical state of the metals in mono and bi-metallic (Fe-EPS, Pd-EPS, FePd-EPS) complexes, by a combination of micro X-ray fluorescence, X-ray absorption spectroscopy methods (XANES and EXAFS), and transmission electron microscopy. The results show that iron in monometallic Fe-EPS and bimetalic FePd-EPS is in the mineralized form of iron oxides/hydroxides, predominantly in the form of Fe3+, with a small amount of Fe2+ in the structure, as a mixture of different nano-crystalline iron oxides and hydroxides. Palladium on the other hand is found as Pd(0) in the form of metallic nanoparticles with fcc structure in both, bi-metallic (FePd-EPS) and mono-metallic (Pd-EPS) species. In bi-metallic species Pd and Fe nanoparticles agglomerate in larger clusters, but they remain spatially separated. Access to the SR facilities at ESRF (beamline ID21, project LS-2225), DESY (beamline C) Hamburg (project I-20110511 EC) and ELETTRA (beamline XAFS, project 20115112) is acknowledged.
Ključne besede: Klebsiella oxytoca, Fe, Pd, XANES, EXAFS, exopolysaccharide, FePd-EPS
Objavljeno v RUNG: 28.06.2016; Ogledov: 7016; Prenosov: 0
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