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3. Non-covalent ligand-oxide interaction promotes oxygen evolutionQianbao Wu, Junwu Liang, Mengjun Xiao, Chang Long, Lei Li, Zhenhua Zeng, Andraž Mavrič, Xia Zheng, Jing Zhu, Matjaž Valant, 2023, izvirni znanstveni članek Opis: Strategies to generate high-valence metal species capable of oxidizing water often employ composition and coordination tuning of oxide-based catalysts, where strong covalent interactions with metal sites are crucial. However, it remains unexplored whether a relatively weak “non-bonding” interaction between ligands and oxides can mediate the electronic states of metal sites in oxides. Here we present an unusual non-covalent phenanthroline-CoO2 interaction that substantially elevates the population of Co4+ sites for improved water oxidation. We find that phenanthroline only coordinates with Co2+ forming soluble Co(phenanthroline)2(OH)2 complex in alkaline electrolytes, which can be deposited as amorphous CoOxHy film containing non-bonding phenanthroline upon oxidation of Co2+ to Co3+/4+. This in situ deposited catalyst demonstrates a low overpotential of 216 mV at 10 mA cm−2 and sustainable activity over 1600 h with Faradaic efficiency above 97%. Density functional theory calculations reveal that the presence of phenanthroline can stabilize CoO2 through the non-covalent interaction and generate polaron-like electronic states at the Co-Co center.
Ključne besede: water oxidation, cobalt hydroxide, ligand-metal interactions
Objavljeno v RUNG: 23.02.2023; Ogledov: 1386; Prenosov: 15
 Celotno besedilo (1,77 MB) |
4. Selenium affects mercury ligand environment in terrestrial food chain – a XAS studyKatarina Vogel Mikuš, Alojz Kodre, Iztok Arčon, Anja Kavčič, 2022, objavljeni povzetek znanstvenega prispevka na konferenci Opis: Selenium (Se) supplied in inorganic form (as selenate or selenite) was shown to decrease mercury (Hg) toxicity by forming HgSe in soils as well as in animal and human tissues, while for plants there is no evidence of Hg-Se complexation. Although Se in not an essential element for plants it was shown to counteract various abiotic stresses when applied at trace amounts. The aim of this work was therefore to study physiological responses and Hg speciation in plant/ fungi-animal food chain. Lettuce (Lactuca sativa) and porcini mushrooms (Boletus edulis) were taken as model plant/ fungal species and Spanish slug (Arion vulgaris) as a model animal species. The plants, fed to the slugs, were grown in HgCl2 contaminated soil or soil from the vicinity of Hg mine in Idrija with traces of HgS and methyl Hg). Physiological parameters of plants and slugs were monitored during the experiment. At the end the biological material was frozen in LN2 and freeze dried. Hg L3-edge (12284 eV) XANES and EXAFS spectra of the biological samples and standards were measured at liquid helium temperature in fluorescence detection mode at the BM30B beamline of the ESRF synchrotron in Grenoble, using the 30-segment germanium solid state detector [1]. The results showed that addition of Se alleviated Hg toxic effects in the food chain started at HgCl2-contaminated soil, while for the soil from Idrija, containing low amounts of highly toxic methyl-Hg, the beneficial effect was less prominent [2]. No Hg-Se complexes were detected in plants, while in mushrooms and slugs the complexation was confirmed. Addition of Se to the plants, however, changed Hg ligand environment in plant tissues from sulphur to nitrogen ligands. Hg and Se both target the -SH functional groups in the plant tissues, so toxic effects of Hg are rather enhanced than alleviated by addition of Se. Nevertheless, the addition of Se to the plants is beneficial for higher trophic levels and lowers Hg toxicity for the primary consumers, the slugs.
Ključne besede: mercury, toxicity, ligand environment, XANES, EXAFS, food chain, plant, slug, fungi
Objavljeno v RUNG: 05.12.2022; Ogledov: 1322; Prenosov: 0
Gradivo ima več datotek! Več... |
5. Impact of stereochemistry on ligand binding : X-ray crystallographic analysis of an epoxide-based HIV protease inhibitorFabio Benedetti, Federico Berti, Pietro Campaner, Lidia Fanfoni, Nicola Demitri, Folasade M. Olajuyigbe, Matteo De March, Silvano Geremia, 2014, izvirni znanstveni članek Ključne besede: stereochemistry, ligand binding, crystallographic analysis
Objavljeno v RUNG: 03.03.2021; Ogledov: 1968; Prenosov: 0
Gradivo ima več datotek! Več... |
6. In silico generation of peptides by replica exchange Monte Carlo: Docking-based optimization of maltose-binding-protein ligandsAnna Russo, Pasqualina Liana Scognamiglio, Rolando Pablo Hong Enriquez, Carlo Santambrogio, Rita Grandori, Daniela Marasco, Antonio Giordano, Giacinto Scoles, Sara Fortuna, 2015, izvirni znanstveni članek Opis: Short peptides can be designed in silico and synthesized through automated techniques, making them advantageous and versatile protein binders. A number of docking-based algorithms allow for a computational screening of peptides as binders. Here we developed ex-novo peptides targeting the maltose site of the Maltose Binding Protein, the prototypical system for the study of protein ligand recognition. We used a Monte Carlo based protocol, to computationally evolve a set of octapeptides starting from a polialanine sequence. We screened in silico the candidate peptides and characterized their binding abilities by surface plasmon resonance, fluorescence and electrospray ionization mass spectrometry assays. These experiments showed the designed binders to recognize their target with micromolar affinity. We finally discuss the obtained results in the light of further improvement in the ex-novo optimization of peptide based binders.
Ključne besede: peptides, docking, optimisation, computation, maltose binding protein, probe, ligand
Objavljeno v RUNG: 12.10.2016; Ogledov: 3962; Prenosov: 140
Celotno besedilo (4,27 MB) |
7. 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: 6163; Prenosov: 0
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