The local structure of gadolinium vanadate–tellurate glasses and glass ceramics: Te2V2O9 crystalline phase

Glasses in the system xGd₂O₃ · (100 − x)[0.7TeO₂ · 0.3V₂O₅] with 0 ≤ x ≤20 mol% have been prepared from melt quenching method. Influence of gadolinium ions on structural behavior in vanadate–tellurate glasses has been investigated using FTIR spectroscopy, X-ray diffraction (XRD), and magnetic susceptibility measurements. The structural changes have been analyzed with increasing rare earth concentration. The structural changes, as recognized by analyzing band shapes of XRD and FTIR spectra, revealed that Gd₂O₃ causes a higher extent of network polymerization as far as 20 mol%. The structure of the heat-treated glasses was found to consist mainly of the Te₂V₂O₉ crystalline phase. These vitreous systems were investigated by magnetic susceptibility measurements. From the paramagnetic susceptibility χ was calculated at different temperature and from the 1/χ(T) graph, the Curie temperature of the glass has been evaluated. Magnetic susceptibility data show the presence of small antiferromagnetic interactions between the Gd⁺³ ions.     

Conformational Isomers of Calcineurin Follow Distinct Dissociation Pathways

In the gas-phase, ions of protein complexes typically follow an asymmetric dissociation pathway upon collisional activation, whereby an expelled small monomer takes a disproportionately large amount of the charges from the precursor ion. This phenomenon has been rationalized by assuming that upon activation, a single monomer becomes unfolded, thereby attracting charges to its newly exposed basic residues. Here, we report on the atypical gas-phase dissociation of the therapeutically important, heterodimeric calcium/calmodulin-dependent serine/threonine phosphatase calcineurin, using a combination of tandem mass spectrometry, ion mobility mass spectrometry, and computational modeling. Therefore, a hetero-dimeric calcineurin construct (62?kDa), composed of CNa (44?kDa, a truncation mutant missing the calmodulin binding and auto-inhibitory domains), and CNb (18?kDa), was used. Upon collisional activation, this hetero-dimer follows the commonly observed dissociation behavior, whereby the smaller CNb becomes highly charged and is expelled. Surprisingly, in addition, a second atypical dissociation pathway, whereby the charge partitioning over the two entities is more symmetric is observed. The presence of two gas-phase conformational isomers of calcineurin as revealed by ion mobility mass spectrometry (IM-MS) may explain the co-occurrence of these two dissociation pathways. We reveal the direct relationship between the conformation of the calcineurin precursor ion and its concomitant dissociation pathway and provide insights into the mechanisms underlying this co-occurrence of the typical and atypical fragmentation mechanisms.     

Hydrodynamics of tsunamis generated by asteroid impact in the Black Sea

Two-dimensional and one-dimensional models are used to evaluate the seashore effects of the tsunami generated by an asteroid hitting the deep water in the Eastern region of the Black Sea. The shallow water theory has been used to describe tsunami propagation. The distance between the impact point and the nearest coast is about 150 km. The effects on the coastal regions depend on many factors among which the most important is asteroid size. The tsunami generated by a 250 m asteroid reaches the nearest dry land location in 20 minutes and needs about two hours to hit all over the Black Sea coast. The horizontal inundation length is also known as run-in or run-off distance, according to the direction of water movement. The run-up values may be up to 39 m in the Eastern basin and a more than ten times smaller in theWestern region. The Northern part of the Black Sea coast is not affected by the tsunami. The run-in values of a tsunami generated by a 1000 m diameter asteroid are sensibly larger than the similar values associated to a 250 m diameter asteroid. The run-in strongly depends on the distance from the impact position to the shore and on coastal topographical profile. For instance, the run-in distance in case of a tsunami generated by a 250 m size asteroid is 0.1 km (at Varna), 0.5 km (Ordu), 0.7 km (Yalta) and 1.4 km (Sochi). In case of the 1000 m diameter asteroid the run-in distance is 0.7 km (at Varna) and 2.9 km (Yalta). The results accuracy is also discussed.     

New synthesis method for M(II) chromites/silica nanocomposites by thermal decomposition of some precursors formed inside the silica gels

In this article, we present a new method for the obtaining of ZnCr₂O₄ and MgCr₂O₄ embedded in silica matrix. This method consists in the formation of Cr(III), Zn(II) and Cr(III), Mg(II) hydroxycarboxylate/carboxylate compounds, during the redox reaction between the nitrate ion and diol (1,3-propanediol), uniformly dispersed in the pores of hybrid gels. The thermal decomposition of these precursors leads to a mixture of corresponding metal oxides. The gels were synthesized starting from mixtures of Cr(NO₃)₃·9H₂O, Zn(NO₃)₂·6H₂O and Cr(NO₃)₃·9H₂O, Mg(NO₃)₂·6H₂O with tetraethyl orthosilicate and 1,3-propanediol for final compositions 50% ZnCr₂O₄/50% SiO₂ and 50% MgCr₂O₄/50% SiO₂. The obtained gels have been thermally treated at 140?°C, when the redox reaction nitrates-diol took place with formation of the precursors within the xerogels pores. The thermal decomposition of all precursors took place up to 300?°C, with formation of oxides mixtures (Cr₂O_3?+?x and ZnO) and (Cr₂O_3?+?x and MgO), respectively. At 400?°C, Cr₂O_3?+?x turn to Cr₂O₃ which reacts with ZnO forming ZnCr₂O₄/SiO₂. Starting with 400?°C, Cr₂O₃ reacts with MgO to an intermediary phase MgCrO₄, which decomposes with the formation of MgCr₂O₄/SiO₂. The formation of the precursors inside the silica matrix and the evolution of the crystalline phases were studied by thermal analysis, FT-IR spectrometry, XRD, and TEM.     

Thermal behaviour and electro-optical properties of a series of liquid crystals based on palladium complexes with mixed ligands

A series of ortho-metallated palladium(II) complexes with two dimeric liquid crystals Schiff base (methoxy and decyloxy as terminal groups) as cyclometallated ligands and N-aryl-N′-benzoyl thiourea derivatives as co-ligands were prepared and investigated for their liquid crystalline properties. Their structures were assigned based on elemental analysis, FT-IR and ¹H NMR spectroscopy while the thermal behaviour was investigated by differential scanning calorimetry and polarising optical microscopy. The complexes with Schiff base ligand bearing methoxy group as terminal group show extensive decomposition during melting while the complexes with Schiff base having decyloxy group as terminal group show monotropic nematic phases, with the mesophase stability strongly related to the type of N-aryl-N′-benzoyl thiourea derivative used. Their liquid crystalline properties are compared with their analogues having N,N-dialkyl-N′-benzoyl thiourea as co-ligands which were reported previously. One of the latter complexes was also investigated by thermally stimulated depolarisation currents method while the optical transmission was recorded simultaneously. The thermally stimulated depolarisation currents and optical transmission spectra confirmed the previous observation regarding the phase transition temperatures. The current intensity–applied voltage dependencies of this complex were investigated by specific electrical measurements.     

New lamellar structure formed by an adamantyl derivative of cholic acid

The self-aggregation of the sodium salt of a new adamantyl amide of the 3beta-amino derivative of cholic acid (Na-AdC) in aqueous solution has been investigated by surface tension, dynamic light scattering, fluorescence, small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM) measurements. These last two techniques suggest that a lamellar phase, consisting of charged bilayers of Na-AdC separated by solvent and periodically stacked, is formed in aqueous solution. The structure of the bilayer is inferred from the resolution of the crystal of the compound in its acid form. The adamantyl moieties, which are mutually interlocked, reside in the central region of the bilayer, and the carboxylic groups are directed toward the hydrophilic region. The structure is open enough to allow water molecules to interact with a fluorescence probe located at the central hydrophobic region.     

Abstract settings for tangential boundary stabilization of Navier–Stokes equations by high- and low-gain feedback controllers

The present paper seeks to continue the analysis in Barbu et al. [Tangential boundary stabilization of Navier–Stokes equations, Memoir AMS, to appear] on tangential boundary stabilization of Navier–Stokes equations, d=2,3$d=2,3$, as deduced from well-posedness and stability properties of the corresponding linearized equations. It intends to complement [V. Barbu, I. Lasiecka, R. Triggiani, Tangential boundary stabilization of Navier–Stokes equations, Memoir AMS, to appear] on two levels: (i) by casting the Riccati-based results of Barbu et al. [Tangential boundary stabilization of Navier–Stokes equations, Memoir AMS, to appear] for d=2,3$d=2,3$ in an abstract setting, thus extracting the key relevant features, so that the resulting framework may be applicable also to other stabilizing boundary feedback operators, as well as to other parabolic-like equations of fluid dynamics; (ii) by including, in the case d=2$d=2$ this time, also the low-level gain counterpart of the results in Barbu et al. [Tangential boundary stabilization of Navier–Stokes equations, Memoir AMS, to appear] with both Riccati-based and spectral-based (tangential) feedback controllers. This way, new local boundary stabilization results of Navier–Stokes equations are obtained over [V. Barbu, I. Lasiecka, R. Triggiani, Tangential boundary stabilization of Navier–Stokes equations, Memoir AMS, to appear].