Separation of Xenon and Krypton in the Metal–Organic Frameworks M2(m-dobdc) (M=Co,Ni)

The separation of Xe and Kr from air is challenging owing both to the very low atmospheric concentrations of these gases and the need for their distillation at cryogenic temperatures. Alternatively, separation processes based on adsorption could provide a less energy-intensive route to the isolation of these gases. Here, we demonstrate that the metal–organic frameworks M₂(m-dobdc) (M=Co, Ni; m-dobdc⁴⁻=4,6-dioxido-1,3-benzenedicarboxylate) effectively separate Xe and Kr at ambient temperatures based on the different adsorption enthalpies of each gas at the coordinatively-unsaturated M²⁺ sites in each material. In situ Xe- and Kr-dosed powder X-ray diffraction studies further reveal key differences in the binding of Xe and Kr within the materials. In particular, while both gases adsorb near the framework open metal sites at 200 K, much higher Xe occupancies are observed at these sites relative to Kr, corroborating a stronger interaction of the polarizing M²⁺ cations with Xe. Further, while krypton is only found located above the open metal sites, two additional adsorption sites are observed for xenon, correlating with the stronger adsorption of Xe over Kr in these materials. These results suggest the possible utility of employing M₂(m-dobdc) materials in the adsorptive separation of Xe and Kr.     

Internalization and Accumulation in Dendritic Cells of a Small pH‐Activatable Glycomimetic Fluorescent Probe as Revealed by Spectral Detection

DC‐SIGN, an antigen‐uptake receptor in dendritic cells (DCs), has a clear role in the immune response but, conversely, can also facilitate infection by providing entry of pathogens into DCs. The key action in both processes is internalization into acidic endosomes and lysosomes. Molecular probes that bind to DC‐SIGN could thus provide a useful tool to study internalization and constitute potential antagonists against pathogens. So far, only large molecules have been used to directly observe DC‐SIGN‐mediated internalization into DCs by fluorescence visualization. We designed and synthesized an appropriate small glycomimetic probe. Two particular properties of the probe were exploited: activation in a low‐pH environment and an aggregation‐induced spectral shift. Our results indicate that small glycomimetic molecules could compete with antigen/pathogen for binding not only outside but also inside the DC, thus preventing the harmful action of pathogens that are able to intrude into DCs, for example, HIV‐1.     

Preliminary investigations of the production of MgAlON bonded refractories

The aim of the work was to find an appropriate composition for the formation of MgAlON bonding phase for Al₂O₃ and MgO based refractories. The first step was the preparation of pure MgAlON. AlN and Al₂O₃ were used as starting powders and either MgO or MgAl₂O₄ was added as a source of magnesium. The results verified the possibility to produce MgAlON under the prevailing conditions. Afterwards, MgAlON bonded alumina and magnesia refractories were investigated. The obtained results confirmed the possibility of the production of MgAlON bonded alumina refractories. However, in the case of magnesia-based samples MgAlON was not formed and instead stoichiometric spinel, AlN and alumina rich spinel were detected in the bonding phase. Additionally, the joining between the MgO grains and the matrix was poor with wide gaps on the interface.     

Nanocrystaline solid solution CeO2–Bi2O3

Nanocrystalline powders of solid solution CeO₂–Bi₂O₃ were synthesized by self-propagating room temperature reaction (SPRT) procedure with composition (Ce_1?xBi_xO_2?δ where the x = 0.1–0.5). X-ray diffraction analyses show that for x < 0.50 a solid solution with fluorite structure is formed. Rietveld's structure refinement method was applied to characterize prepared powders and its microstructure (size–strain). The lattice parameters increase according to Vegard's rule with increasing of Bi concentration. The average crystallite size is about 2–3 nm. Spectroscopic ellipsometry and Raman scattering measurements were used to characterize the samples at room temperature. The Raman measurements demonstrated electron molecular vibrational coupling and increase of oxygen vacancy concentration whereas increase of Bi content provokes a small decrease of optical absorption edge in comparison with pure ceria. Specific surface area of obtained powders was measured by Brunauer–Emmet–Teller (BET) method.     

The effect of nano-structured alumina coating on the bond strength of resin-modified glass ionomer cements to zirconia ceramics

The purpose of this study was to evaluate the effect of Y-TZP ceramic surface functionalization with a nano-structured alumina coating on bond strength of the resin modified glass ionomer dental cement. A total of 160 disc-shaped specimens were produced and randomly divided into two groups of 80. Half of the discs in each group received an alumina coating which was fabricated by exploiting the hydrolysis of aluminum nitride (AlN) powder. The shear bond strengths of the resin-modified glass ionomer cement FUJI+ (GC Japan) and the composite resin luting agent RelyX Unicem (3M ESPE, USA) were then studied for the coated and uncoated surfaces The SEM analyses revealed that the application of an alumina coating to the Y-TZP ceramics created a highly retentive surface for bonding. The bond strengths for the coated groups in both cements were significantly higher than the uncoated groups.     

Luminescence during anodization of magnesium alloy AZ31

In this paper, we have presented our recent investigation of luminescence during anodization of magnesium alloy AZ31 at 100 mA/cm² in water solution containing 4 g/L Na₂SiO₃·5H₂O + 4 g/L KOH. Spectral characterization of anodic luminescence (galvanoluminescence GL) showed that there are wide GL bands in the range from 375 nm to 875 nm, with three spectral peaks around 430 nm, 600 nm and 780 nm. As the anodization voltage approaches the breakdown voltage, a large number of microdischarges appear superimposed on the GL. The microdischarges characteristics above breakdown (so-called plasma electrolytic oxidation PEO) were studied using real-time imaging. The spatial density of microdischarges is the highest in the early stage of PEO, while the percentage of oxide coating area covered by active discharge sites has maximum after about 120 s from the beginning of PEO and then stays almost constant. The elements present in PEO microdischares were identified using optical emission spectroscopy technique.     

Stereometric analysis of nanostructured boehmite coatings synthesized by aluminum nitride powder hydrolysis

We studied the morphological properties of precipitated, nanostructured, boehmite coatings on a polished alumina surface by exploiting the aluminum nitride (AlN) powder hydrolysis at elevated temperatures. The hydrolysis tests of the 3 wt% AlN powder suspensions in the temperature range 50–90 °C were performed in order to estimate the time needed for the synthesis of the coatings. They consisted of interlocked boehmite lamellas, positioned perpendicularly to the ceramic surface, and they exhibited a strong temperature-dependent size and surface density. The aim of this research was a quantitative assessment of the as-formed boehmite coatings. Based on electron microscopy micrographs, a stereometric analysis of the as-prepared coatings was performed in order to estimate the relevant geometric parameters of the lamellas. In spite of the temperature-dependent lamellas’ size and surface density, the specific volume of the coatings was similar for all the synthesis temperatures.     

Early stages of growth of gold layers sputter deposited on glass and silicon substrates

Extremely thin gold layers were sputter deposited on glass and silicon substrates, and their thickness and morphology were studied by Rutherford backscattering (RBS) and atomic force microscopy (AFM) methods. The deposited layers change from discontinuous to continuous ones for longer deposition times. While the deposition rate on the silicon substrate is constant, nearly independent on the layer thickness, the rate on the glass substrate increases with increasing layer thickness. The observed dependence can be explained by a simple kinetic model, taking into account different sticking probabilities of gold atoms on a bare glass substrate and regions with gold coverage. Detailed analysis of the shape of the RBS gold signal shows that in the initial stages of the deposition, the gold layers on the glass substrate consist of gold islands with significantly different thicknesses. These findings were confirmed by AFM measurements, too. Gold coverage of the silicon substrate is rather homogeneous, consisting of tiny gold grains, but a pronounced worm-like structure is formed for the layer thickness at electrical continuity threshold. On the glass substrate, the gold clusters of different sizes are clearly observed. For later deposition stages, a clear tendency of the gold atoms to aggregate into larger clusters of approximately the same size is observed. At later deposition stages, gold clusters of up to 100 nm in diameter are formed.     

Antiproliferative and Proapoptotic Activities of Methanolic Extracts from Ligustrum vulgare L. as an Individual Treatment and in Combination with Palladium Complex

The aim of this study is to examine the growth inhibitory effects of methanolic leaf and fruit extracts of L. vulgare on HCT-116 cells over different time periods and their synergistic effect with a Pd(apox) complex. The antiproliferative activity of plant extracts alone or in combination with the Pd(apox) complex was determined using MTT cell viability assay, where the IC(50) value was used as a parameter of cytotoxicity. Results show that antiproliferative effects of L. vulgare extracts increase with extension of exposure time, with decreasing IC(50) values, except for 72 h where the IC(50) values for methanolic leaf extract were lower than for the fruit extract. The Pd(apox) complex alone had a weak antiproliferative effect, but combination with L. vulgare extracts caused stronger effects with lower IC(50) values than with L. vulgare extracts alone. The type of cell death was explored by fluorescence microscopy using the acridin orange/ethidium bromide method. Treatments with plant extracts caused typical apoptotic morphological changes in HCT-116 cells and co-treatments with Pd(apox) complex caused higher levels of apoptotic cells than treatment with plant extracts alone. The results indicate that L. vulgare is a considerable source of natural bioactive substances with antiproliferative activity on HCT-116 cells and which have a substantial synergistic effect with the Pd(apox) complex.     

The A9 Core Sequence from NRPS Adenylation Domain Is Relevant for Thioester Formation

The adenylation (A) domain in nonribosomal peptide synthetases catalyses a two-step reaction in which an amino acid is activated and then transferred to the neighbouring thiolation (T) domain. In this study, we investigated the role of the conserved A9 core sequence of the A-domain of tyrocidine synthetase 1, by analysis of single amino acid mutations in the A9 region. Mutation of an absolutely conserved proline (P490G) significantly reduced the conformational stability of the protein, as evidenced by increased susceptibility to proteolytic cleavage and denaturation. All mutant A-domains were capable of amino acid activation, but the activity in the overall reaction was reduced. Surprisingly, the S491R mutant (mutation at the first residue following the A9 motif) showed elevated overall activity compared to the wild-type protein. Our results suggest that the A9 core sequence plays a role in the second reaction step, in which it could serve as a "clip" for the proper positioning of residues important for the interaction with the T-domain, and/or stabilisation of the thioester-forming conformation.