Aqueous sol–gel synthesis and thermoanalytical study of the alkaline earth molybdate precursors

The preparation and characterization of the M′–Mo–O nitrate–tartrate (M′ = Mg, Ca, Sr, and Ba) gels, which were produced by the simple aqueous sol–gel method and calcined at 500, 600, 700, 800, 900, and 1,000 °C temperatures are reported. The crystalline alkaline earth metal molybdates (MgMoO₄, CaMoO₄, SrMoO₄, and BaMoO₄) and as-prepared M′–Mo–O nitrate–tartrate gels investigated by thermal analysis (TG/DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM). TG/DSC analysis showed the possible decomposition mechanism of synthesized gels. XRD studies allowed the identification of main types of crystalline structures in the MgMoO₄, CaMoO₄, SrMoO₄, and BaMoO₄ systems. Moreover, SEM analysis revealed the changes of surface morphology of the final compounds depending on annealing temperatures.     

N-Aryl-N-Hydroxy Urethanes as Peroxidase Substrates

 N-Aryl-N-hydroxy urethanes (AHUs), which are promising N*OH mediators for oxidoreductase catalysis, are electrochemically active redox compounds with a redox potential of 0.35–0.40 V vs. SCE (0.59–0.64 V vs. NHE). Alkyl substituents in the carbamic acid residue have, as expected, only little influence on the redox potential. The highest potential was noticed for N-hydroxy-N-(4-cyanophenyl)-carbamic acid methyl ester. Recombinant Coprinus cinereus peroxidase (rCiP) catalyzes oxidation of the AHUs with apparent bimolecular constants k _ox of 2.5ċ10⁴–7.5ċ10⁴ M ⁻¹s⁻¹ at pH = 8.5 and 25°C. Structure-function connectivities of the substrates were analysed within the framework of the Marcus cross relationship and by using ab initio quantum chemical calculations. An excellent correlation of the redox potentials and the HOMO energies could be found. However, no correlation of log(k _ox) with redox potential and HOMO energy was indicated as predicted by theory. This was explained by specific docking of the substrates in the active center of rCiP.     

Elastic properties of chemically modified baker's yeast cells studied by AFM

Chemical pretreatment is widely used to facilitate transformation of living cells when foreign components are introduced into a cell through the cell wall. The influence of appropriate chemicals on the wall properties and mechanism of transformation is still a matter of intensive studies. Saccharomyces cerevisiae cells (also known as baker's yeast) were investigated by atomic force microscopy (AFM). The cell walls were modified by lithium acetate and dithiothreitol. The AFM imaging was performed in liquid water‐based environment. The living cells were fixed by trapping into the holes of a polycarbonate membrane. Mechanical and morphological properties of initial intact cells and treated cells were investigated. The increased stiffness of the chemically treated cells was observed. As deduced from the applied theoretical Hertz‐Sneddon model, the treated cells show completely different response mechanism to applied mechanical pressure in comparison with the intact cells. Also, the increased roughness of the cell wall of the treated yeasts was observed. Copyright © 2011 John Wiley & Sons, Ltd.     

On the fractional parts of the natural powers of a fixed number

Let ξ ≠ = 0 and α > 1 be reals. We prove that the fractional parts {ξ αⁿ}, n = 1, 2, 3, ..., take every value only finitely many times except for the case when α is the root of an integer: α = q ^1/d, where q ≥ 2 and d ≥ 1 are integers and ξ is a rational factor of a nonnegative integer power of α.     

Arithmetical Properties of Powers of Algebraic Numbers

We consider the sequences of fractional parts {ⁿ}, n = 1, 2,3,..., and of integer parts [ⁿ], n = 1, 2, 3,..., where isan arbitrary positive number and > 1 is an algebraic number.We obtain an inequality for the difference between the largestand the smallest limit points of the first sequence. Such aninequality was earlier known for rational only. It is alsoshown that for roots of some irreducible trinomials the sequenceof integer parts contains infinitely many numbers divisibleby either 2 or 3. This is proved, for instance, for , n = 1, 2, 3,.... The fact that thereare infinitely many composite numbers in the sequence of integerparts of powers was proved earlier for Pisot numbers, Salemnumbers and the three rational numbers 3/2, 4/3, 5/4, but nosuch algebraic number having several conjugates outside theunit circle was known. 2000 Mathematics Subject Classification11J71, 11R04, 11R06, 11A41.     

Investigation of Structural and Luminescent Properties of Sol-Gel-Derived Cr‑Substituted Mg3Al1−xCrx Layered Double Hydroxides

In the present work, Cr-substituted Mg₃Al_1−xCr_x layered double hydroxides (LDHs) were synthesised through the phase conversion of sol-gel-derived mixed-metal oxides in an aqueous medium. The chromium substitution level in the range of 1 to 25 mol% was investigated. It was demonstrated that all synthesised specimens were single-phase LDHs. The results of elemental analysis confirmed that the suggested synthetic sol-gel chemistry approach is suitable for the preparation of LDHs with a highly controllable chemical composition. The surface microstructure of sol-gel-derived Mg₃Al_1−xCr_x LDHs does not depend on the chromium substitution level. The formation of plate-like agglomerated particles, which consist of hexagonally shaped nanocrystallites varying in size from approximately 200 to 300 nm, was observed. Optical properties of the synthesised Mg₃Al_1−xCr_x LDHs were investigated by means of photoluminescence. All Cr-containing powders exhibited characteristic emission in the red region of the visible spectrum. The strongest emission was observed for the sample doped with 5 mol% Cr³⁺ ions. However, the emission intensity of samples doped with 1–10 mol% Cr³⁺ ions was relatively similar. A further increase in the Cr³⁺ ion concentration to 25 mol% resulted in severe concentration quenching.     

Preparation by different methods and analytical characterization of gadolinium-doped ceria

The present work reports the influence of chemical synthesis on structural, morphological and optical properties of gadolinium-doped ceria (GDC) with analytical characterization of synthesized specimens. GDC powders with Gd content of 10, 15 and 20 mol% were synthesized by aqueous sol–gel and sol–gel combustion methods using glycerol as complexing agent and fuel. The phase purity and structural features of obtained powders were evaluated using X-ray diffraction analysis and Raman spectroscopy. These studies confirmed that crystallization of GDC occurs into cubic fluorite-type crystal structure. Morphological features as well as optical properties of GDC powders were determined to be strongly dependent on the synthesis method. To confirm chemical composition of prepared samples, spectrophotometric approach for the determination of Ce and Gd in GDC samples was suggested. Relative standard deviation values for Ce and Gd were in the range of 1.5–4.1 and 2.0–5.6%, respectively. The obtained results demonstrated that the suggested analytical procedure can be successfully used for the analysis of GDC specimens with high accuracy.