Crystal structure and spectroscopic characterization of K8(VO)2O(SO4)6

Red and yellow dichroistic crystals of a vanadium(V) compound, potassium (mu-oxo, di-mu-sulfato)bis(oxodisulfatovanadate), K(8)(VO)(2)O(SO(4))(6), have been obtained from the ternary catalytic model melt system K(2)S(2)O(7)[bond]K(2)SO(4)[bond]V(2)O(5). By slow cooling of the melt from 420 to 355 degrees C, crystal growth occurred, using solid V(2)O(5) crystals present in the melt as nucleation promoter. The compound crystallizes in the monoclinic space group P2(l) with a = 13.60(9) A, b = 13.93(9) A, c = 14.05(9) A, beta = 90.286(10) degrees, and Z = 2. It contains two VO(6) octahedra linked together by a mu-oxo and two mu-sulfato bridges. Furthermore, each octahedron has two monodentate sulfate ligands, making the dimeric entity coordinatively saturated. IR spectroscopy shows bands arising from V[bond]O[bond]V and V[double bond]O stretches as well as splitting of sulfate bands due to the different degrees of freedom present for different conformations of sulfate ligands. The coordination of vanadium in K(8)(VO)(2)O(SO(4))(6) is discussed in relation to the reaction mechanism of SO(2) oxidation catalysis.     

Ein weiterer Beitrag zum Scandiumdicarbidproblem

Zusammenfassung Die bei 1850, 2000 bzw. 2300°C durch die Reduktion von Scandiumoxid mittels Kohlenstoff in dem der Scandiumdicarbidbildung entsprechenden Molverhältnis hergestellten Produkte wurden mit Wasser zersetzt und mit Hilfe der gleichzeitigen gaschromatographischen und massenspektrometrischen Analyse untersucht. Aus den Ergebnissen geht hervor, daß bei der Scandiumdicarbidbildung gleichzeitig ein weiteres Scandiumcarbid, höchstwahrscheinlich ein Sesquicarbid, entsteht.

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Scandium(III) dicarbide problem. Further experimental results

Products obtained by the reduction of Sc₂O₃ with carbon at 1850, 2000 and 2300°C, resp., in the molar ratio corresponding to the scandium dicarbide were hydrolysed with water. Gaseous reaction products were analysed using gas chromatography combined with mass spectrometry. Results show, that during dicarbide formation another scandium carbide, probably sesquicarbide, is also formed.

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Herrn Prof. Dr.H. Nowotny gewidmet.

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7. Mitt.: Coll. Czech. Chem. Commun., im Druck.     

Phase Equilibria in the Ni–Al–W System at 900°C

Multicomponent Ni-base alloys exhibit good mechanical properties even at elevated temperatures and they are widely used for industrial production of exertion-resistive parts of engines. These properties are mainly determined by the coexistence of a disordered γ matrix with a face centred cubic lattice and cuboidal domains of its ordered γ′ structure. Therefore it is useful to study phase equilibria in Ni-base systems, namely in the regions involving both mentioned phases. One of the conclusions of our recent work on Ni–Al–Cr–W system was a necessity of modification of selected thermodynamic parameters of the ternary Ni–Al–W subsystem in order to achieve a better agreement of our experimental observations with theoretical modelling. This involves new measurements of the microstructure of selected samples of the Ni–Al–W system at 900°C and the comparison of the results with existing literature data in order to confirm our conclusions on higher order system investigated before. It is a first step on the way to an assessment of the Ni–Al–W system, which has not been done before.     

Phase transitions in ternary caesium lead bromide

Phase transitions in ternary caesium lead bromide (CsPbBr₃) were studied by means of DSC, TMA and high temperature X-ray diffraction. The samples were prepared from the solution by water evaporation and from the melt. on the DSC curves as well as on the temperature dependence of the lattice constants of CsPbBr₃ only two effects were found belonging to the earlier published phase transitions at 88 and 130°C and no further effects. Linear thermal expansion coefficient α of individual CsPbBr₃ modifications were calculated from both TMA and high temperature X-ray diffraction. The structural parameters of the room temperature orthorhombic phase were refined and the results are presented. CsPbBr₃ prepared from the solution contained about 10% of CsPb₂Br₅ and so the DSC curve of pure CsPb₂Br₅ was also measured and an effect at a temperature of 68.5°C was found. This revised version was published online in July 2006 with corrections to the Cover Date.     

Biocompatible hydrogels based on chitosan,cellulose/starch,PVA and PEDOT:PSS with high flexibility and high mechanical strength

Fabricating mechanically strong hydrogels that can withstand the conditions in internal tissues is a challenging task. We have designed hydrogels based on multicomponent systems by combining chitosan, starch/cellulose, PVA, and PEDOT:PSS via one-pot synthesis. The starch-based hydrogels were homogeneous, while the cellulose-based hydrogels showed the presence of cellulose micro- and nanofibers. The cellulose-based hydrogels demonstrated a swelling ratio between 121 and 156%, while the starch-based hydrogels showed higher values, from 234 to 280%. Tensile tests indicated that the presence of starch in the hydrogels provided high flexibility (strain at break?>?300%), while combination with cellulose led to the formation of stiffer hydrogels (elastic moduli 3.9–6.6 MPa). The ultimate tensile strength for both types of hydrogels was similar (2.8–3.9 MPa). The adhesion and growth of human osteoblast-like SAOS-2 cells was higher on hydrogels with cellulose than on hydrogels with starch, and was higher on hydrogels with PEDOT:PSS than on hydrogels without this polymer. The metabolic activity of cells cultivated for 3 days in the hydrogel infusions indicated that no acutely toxic compounds were released. This is promising for further possible applications of these hydrogels in tissue engineering or in wound dressings.

Graphical abstract

     

A stereochemical anomaly: the cyclised (R)-AMPA analogue (R)-3-hydroxy-4,5,6,7-tetrahydroisoxazolo[5,4-c]pyridine-5-carboxylic acid [(R)-5-HPCA] resembles (S)-AMPA at glutamate receptors

(RS)-3-Hydroxy-4,5,6,7-tetrahydroisoxazolo[5,4-c]pyridine-5-carboxylic acid (5-HPCA)(), which is a conformationally constrained cyclised analogue of AMPA has previously been described as causing glutamate receptor mediated excitations of spontaneously firing cat spinal interneurons in a similar fashion to AMPA. We have now prepared the enantiomers of through chiral chromatographic resolution of (RS)-3-(carboxymethoxy)-4,5,6,7-tetrahydroisoxazolo[5,4-c]pyridine-5-carboxylic acid () followed by a stereoconservative hydrolysis resulting in the enantiomers of with high enantiomeric excess (% ee [greater-than-or-equal] 99). The absolute configurations indicated by an X-ray analysis of (-)- monohydrate were confirmed by comparing observed and ab initio calculated electronic circular dichroism spectra and by stereoconservative synthesis of (S)- from (S)-AMPA, the pharmacologically active form of AMPA. The pharmacological effects at native and cloned (GluR1-4) AMPA receptors were shown to reside exclusively with (R)-(+)-, in striking contrast to the usual stereoselectivity trend among AMPA receptor agonists. The reasons for this anomalous behaviour became clear upon docking both enantiomers of to the agonist binding site of GluR2.     

Nanofibers prepared by electrospinning from solutions of biobased polyamide 4

A successful preparation of polyamide 4 nanofibers via electrostatic spinning with diameters close to 100 nm is described. Polyamide 4 was prepared by the anionic ring‐opening polymerization of 2‐pyrrolidone and characterized. The effect of the system parameters (i.e., molar mass of the polymer, the solvent system) and the process parameters (i.e., the electrode‐to‐collector distance) during the electrostatic spinning have been studied. The morphology of the polyamide 4 fiber layers is given except molar mass of the polymer and the concentration of its solution primarily by the conformation of polyamide chains due to polyelectrolyte effect which was confirmed by viscosity measurements. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2203–2210     

Summary of ISO/TC 201 Standard: ISO 22415—Surface chemical analysis—Secondary ion mass spectrometry—Method for determining yield volume in argon cluster sputter depth profiling of organic materials

The International Standard ISO 22415 provides methods to measure sputtering yield volumes of organic test materials using argon cluster ions. The test materials should consist of thin films of known thicknesses between 50 and 1000 nm. The format of the test materials, the measurement of sputtering ion dose, sputtered depth, and reporting requirements for sputtering yield volumes are described.     

A critical analysis of the effect of crosslinking on the linear viscoelastic behavior of styrene–butadiene rubber and other elastomers

The linear viscoelastic behavior in dynamic shear and tensile creep at temperatures from −30 to 70 °C is measured for an styrene–butadiene rubber (SBR) elastomer cured with dicumyl peroxide to crosslinking densities between 0 and 23.5 × 10⁻⁵ mol/cm³. The G′, G″, and tan δ isotherms are analyzed by time–temperature superposition (TTS), where the tan δ master curves are consistent with those of Mancke and Ferry. However, to achieve the TTS in the lightly crosslinked SBR systems, an anomalous vertical shift is required in the narrow temperature region from 10 to 30 °C. The vertical shift factor in this temperature region is not the standard from rubber elasticity. No anomalous behavior is detected in the equilibrium modulus, which is a linear function of temperature in accordance with the classical theory of rubber elasticity. In contrast to SBR, standard vertical shifts are required to effect TTS for uncrosslinked polybutadiene and an ethylene propylene diene monomer elastomer. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013