Computational study of cation substitutions in apatites

Density-functional theory plane-wave modeling of fluor- and hydroxyapatites has been performed, where one or two calcium ions per unit cell were replaced with cadmium or zinc cations. It was found that cadmium ions favor Ca(1) positions in fluorapatites and Ca(2) positions in hydroxyapatites, in agreement with experiment. A similar pattern is predicted for zinc substitutions. In the doubly substituted cases, where only hydroxyapatites were modeled, a preference for the substituting ions to be located in Ca(2) position was also observed. Displacement of the hydroxide ions from their symmetrical positions on the hexagonal axis can be used to explain the preferred configurations of substituting ions around the axis.     

Molecular evolution using intramolecular acyl migration on myo-inositol benzoates with thermodynamic and kinetic selectors

A molecular evolution model was successfully demonstrated by combining the intramolecular acyl migration on inositol tribenzoates and boron selectors. The addition of boric acid to 12 members of DCL (dynamic combinatorial library) induced the dramatic amplification of myo-I(2,4,6)Bz(3) (1) with up to 94 % under thermodynamic (see Figure 1 c) control while a portion of phenyl boronic acid caused two significant different distributions: under kinetic control, the pre-equilibrium of DCL shifted to induce the exclusive amplification of 1,4,6-tribenzoyl myo-inositol (7) with decrease of other members up to 82 % from the mixture (see Figure 2 b), and changed gradually to form 2,4,6-tribenzoyl myo-inositol (1) with up to 96 % under thermodynamic control (Figure 2 c).     

Preparation of colored latex with polyurea shell by miniemulsion polymerization

Colored latexes with polyurea shell were prepared by applying interfacial polycondensation reaction to the miniemulsion polymerization process. These colored latexes were composed of polystyrene core and polyurea shell, and their particle size was adjusted to <100 nm. Diisocyanate was used as a hydrophobic monomer, and the equivalent mole of diamine was used as a hydrophilic monomer for interfacial polymerization. It was important to control the rate of interfacial polycondensation reaction in order to prepare small particles. Dye preservation property of colored latex loaded with oil-soluble dye was investigated. Polyurea shell formed at the surface of latex particles could restrain the migration of dyes from the latex particles and improve the dye preservation property. The ability to prevent dye migration depended on the composition of the polyurea shell.     

Long-term performance of poly(vinyl chloride) cables. Part 1: Mechanical and electrical performances

Cables insulated with plasticized poly(vinyl chloride) were aged in air at temperatures between 80 °C and 180 °C and their conditions were assessed by indenter modulus measurements, tensile testing, infrared (IR) spectroscopy and differential scanning calorimetry (DSC). Electrical testing of oven-aged cable samples was performed in order to relate the electrical functionality during a high-energy line break (HELB) to the mechanical properties and to establish a lifetime criterion. The mechanical data taken at room temperature after ageing could be superimposed with regard to ageing time and temperature. The ageing-temperature shift factor showed an Arrhenius temperature dependence. The jacketing material showed an immediate increase in stiffness (indenter modulus and Young's modulus) and a decrease in the strain at break on ageing; these changes were dominated by loss of plasticizer by migration which was confirmed by IR spectroscopy and DSC. The core insulation showed smaller changes in these mechanical parameters; the loss of plasticizer by migration was greatly retarded by the closed environment, according to data obtained by IR spectroscopy and DSC, and the changes in the mechanical parameters were due to chemical degradation (dehydrochlorination). A comparison of data obtained from this study and data from other studies indicates that extrapolation of data for the jacketing insulation can be performed according to the Arrhenius equation even down to service temperatures (20-50 °C). The low-temperature deterioration of the jacketing is, according to this scheme, dominated by loss of plasticizer by migration.     

Mechanism of 2-O→3-O silyl migration in cyclomaltohexaose (α-cyclodextrin)

To gain insight into the mechanism of the well-known 2-O→3-O silyl migration of 2-O-silylated cyclomaltooligosaccharides (cyclodextrins) under basic conditions, we have undertaken studies of the reaction of 2^A-O-TBDMSi-6^A-deoxy-6^A-S-phenyl-α-cyclodextrin with MeI and NaH. Under these conditions, the TBDMSi group on the C-2 oxygen was found to migrate onto the C-3 oxygen in the glucose residue in which the C-2 oxygen is located, and not onto the C-3 oxygen in the adjacent glucose residue.     

Coupling of propargylsilanes with Fischer carbene chromium complexes: a new synthesis of conjugated dienes

The reaction of propargylsilanes with Fischer carbene complexes has been examined. If the silane-containing carbon is secondary the predominant pathway involves formation of conjugated dienes through a 1,2-silicon shift process of the initially formed vinylcarbene complex intermediate. If a primary propargylsilane is employed, the silicon does not shift and normal alkyne-Fischer carbene coupling processes are observed. The process is moderately stereoselective, resulting in the E enol ether and Z alkenylsilane.     

竖置多孔填料床内热湿迁移特性研究

通过对气相达西阻力的定义,提出了更准确、更完善地反映多孔介质内部热质传递现象的“三态-六场”模型,并以此模型对竖置多孔填料床内的热质交换过程进行了数值模拟,分析了典型工况下填料床内部各物理量场的变化规律.计算及分析结果一方面表明了模型的可行性,另一方面也表明竖直多孔窗比水平多孔窗具有更好的蒸发制冷效果.     

Improvement of the storage stability and photostability of colored latex prepared by miniemulsion polymerization

Polymer particles containing oil-soluble dyes (colored latex) were prepared by miniemulsion polymerization. The dye preservation properties of colored latex loaded with different types of dye were studied; preservation depended on the rate of dye diffusion and thus on the size of the dye molecules and the hardness of the polymer matrix in the latex particles. Hindered amine stabilizers (HAS) were used to improve the photostability of colored latex. The effect of HAS in colored latex was investigated both as an additive and as a comonomer. The photostability of latex particles containing a simple mixture of dye and HAS was improved with increasing HAS content up to 20% in particles. In the case of colored latex particles combined with HAS by a covalent bond, the optimal amount of HAS for photostability improvement was between 8 and 20%.     

Determination of antioxidants by solid-phase extraction method in aqueous food simulants

An analytical method for the determination of specific migration levels of phenolic antioxidants and one phosphite antioxidant in the aqueous food simulants established by European legislation has been developed. This method involves solid-phase extraction (SPE) of the antioxidants with silica C₁₈ cartridge and their determination by liquid chromatography (LC) with diode-array detection. The achieved results in the studies of elution volume determination, breakthrough volume and accuracy are showed. Recoveries in the range of 78–104% and a relative standard deviation between 2.0 and 7.7% have been achieved.     

Decay Curve Analysis of Alkali-Silicate Glass Exposed to Electrons

 Binary and ternary potassium, rubidium and caesium glasses were irradiated by an electron beam with energy varying from 10 to 50 keV. Alkali ion X-ray decays were recorded and afterward incubation periods were determined. The incubation period versus electron energy curves revealed thresholds, which are typical for each alkali species. The threshold ratios are proportional to the mass of the alkali species, consistent with the suggested elastic scattering assisted hopping mechanism.