An approach to alicyclic ring-fused xanthines

A convenient three-step approach to the synthesis of five to eight-membered alicyclic ring-fused xanthines was developed. The method included reaction of lactim or thiolactim ethers with 6-aminouracils, followed by bromination and copper-catalyzed arylation. The procedure allowed preparation of the title compounds in 21–36% overall yields.     

Physisorption of N2, O2, and CO on fully oxidized TiO2(110)

Physisorption of N(2), O(2), and CO was studied on fully oxidized TiO(2)(110) using beam reflection and temperature-programmed desorption (TPD) techniques. Sticking coefficients for all three molecules are nearly equal (0.75 +/- 0.05) and approximately independent of coverage suggesting that adsorption occurs via a precursor-mediated mechanism. Excluding multilayer coverages, the TPD spectra for all three adsorbates exhibit three distinct coverage regimes that can be interpreted in accord with previous theoretical studies of N(2) adsorption. At low coverages (0-0.5 N(2)/Ti(4+)), N(2) molecules bind head-on to five-coordinated Ti(4+) ions. The adsorption occurs preferentially on the Ti(4+) sites that do not have neighboring adsorbates. This arrangement minimizes the repulsive interactions between the adsorbed molecules along the Ti(4+) rows resulting in a relatively small shift of the TPD peak (105 --> 90 K) with increasing coverage. At higher N(2) coverages (0.5-1.0 N(2)/Ti(4+)) the nearest-neighbor Ti(4+) sites become occupied. The close proximity of the adsorbates results in strong repulsion thus giving rise to a significant shift of the TPD leading edges (90 --> 45 K) with increasing coverage. For N(2)/Ti(4+) > 1, an additional low-temperature peak (approximately 43 K) is present and is ascribed to N(2) adsorption on bridge-bonded oxygen rows. The results for O(2) and CO are qualitatively similar. The repulsive adsorbate-adsorbate interactions are largest for CO, most likely due to alignment of CO dipole moments. The coverage-dependent binding energies of O(2), N(2), and CO are determined by inverting TPD profiles.     

Stereochemical and regiochemical trends in the selective detection of saccharides

Several discreet sugar-boronate complexes exist in solution. This is due to the complex equilibria between isomeric species of even the simplest monosaccharides. In the current investigation, we determine the regio- and stereochemical features of the various equilibrating sugar isomers that induce signal transduction in boronic acid chemosensors such as 1 as well as 2 and 3. We present a unique example of a chemosensor (1) that is selective for ribose, adenosine, nucleotides, nucleosides, and congeners. As a result of this study, we are able to predict and achieve selective fluorescence and colorimetric responses to specific disaccharides as a consequence of their terminal sugar residue linkage patterns and configurations. We also find that the combined use of chemosensors exhibiting complementary reactivities may be used cooperatively to obtain enhanced selectivity for ribose and rare saccharides.     

Micromechanical creep model for pure copper

A Unit Cell made of copper is simulated and investigated under creep conditions within the framework of micromechanics. Geometrical 3D model of the copper microstructure is represented as a Unit Cell with grains of random crystallographical orientation and geometry. Such simulation enables algorithm of Voronoi tessellation. The stress-strain behavior of grains in the general case is anisotropic due to the ordered crystalline structure. The anisotropic model for a material with a cubic symmetry is implemented in Abaqus and used to assign behavior of grain interior in elastic and creep regions. Material parameters for elastic model are taken from elastic tests of single crystal copper [1]. Power law material parameters for creep model are taken from creep test performed for single crystal copper [2]. The model parameter ξ is validated numerically. Creep results are presented for the case of proportional loading during the primary and secondary creep. Statistical analysis of creep curves received for 55 different realizations of Unit Cell geometry is carried out. As a result confident interval and mathematical expectation of creep data are calculated. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Shape preserving approximation on the real line with exponential weights

The well-known “Bernstein’s weighted problem” deals with the possibility of weighted approximation on the whole real line. In this paper, we show the possibility of k-monotone approximation on the real line with Freud’s weight .     

Creep damage modeling of a polycrystalline material

A polycrystalline material is investigated under creep conditions within the framework of continuum micromechanics. Geometrical 3D model of a polycrystalline microstructure is represented as a unit cell with grains of random crystallographical orientation and shape. Thickness of the plains, separating neighboring grains in the unit cell, can have non-zero value. Obtained geometry assigns a special zone in the vicinity of grain boundaries, possessing unordered crystalline structure. A mechanical behavior of this zone should allow sliding of the adjacent grains. Within the grain interior crystalline structure is ordered, what prescribes cubic symmetry of a material. The anisotropic material model with the orthotropic symmetry is implemented in ABAQUS and used to assign elastic and creep behavior of both the grain interior and grain boundary material. Appropriate parameters set allows transition from the orthotropy to the cubic symmetry for the grain interior. Material parameters for the grain interior are identified from creep tests for single crystal copper. Model parameters for the grain boundary are set from the physical considerations and numerical model validation according to the experimental data of the grain boundary sliding in a polycrystalline copper [2]. As the result of analysis representative number of grains and grain boundary thickness in the unit cell are recommended. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Amination of brominated nanoporous activated carbon beads for the preparation of CO2 adsorbents

Abstract

Nanoporous activated carbon (NAC) beads that prepared by carbonization of microporous polymer 2,6-di-tert-butyl pyridine beads were subjected to bromination followed by amination to synthesize the NAC derivatives carrying amino groups. Grafted bromine groups, 0.41?mmol of Br per 1?g of NAC, are hydrolytic stable at 100 °С and can be successfully substituted by amino groups. SEM, TEM, and texture studies were shown a nanoporosity decrease. However, the aminated NAC beads maintained a narrow nanopore size distribution and high specific surface area, retaining a spherical shape. These beads were evaluated for capturing CO₂ and showed good reversible adsorption capacity. The preparation method can easily be scaled up, and the NAC beads can be used for other adsorption applications where shaped carbon solids with developed nanoporosity are required.     

Interior continuity,continuity up to the boundary,and Harnack's inequality for double-phase elliptic equations with nonlogarithmic conditions

We prove continuity and Harnack's inequality for bounded solutions to elliptic equations of the type under the precise choice of μ.