Selectively protected galactose derivatives for the synthesis of branched oligosaccharides

Synthesis and characterization of several new anomerically pure galactose derivatives, based on simple and effective protective group manipulations of benzyl β-d-galactopyranoside, are reported. The monosaccharides described contain selectively protected/deprotected hydroxyl functionalities at their 1,2,3,4- and 6-positions rendering them useful as building blocks for construction of branched oligosaccharides.     

Dynamics of the surface layer in cyanobiphenyl-aerosil nanocomposites with a high silica density

Composites were prepared from an aerosil and 4-n-alkyl-4'cyanobiphenyls with five to eight carbon atoms in the alkyl chain. Their high silica density of ∼7 g aerosil in 1 cm³ of liquid crystal (LC) allows the observation of the behaviour of a thin cyanobiphenyl layer (having nearly a monolayer structure) on the silica particles. The systems are investigated by dielectric spectroscopy (10^-2-10⁹ Hz) in a large temperature range (220-370 K). All the composites show a (main) relaxation process at frequencies much lower than the processes observed for the bulk LC that was assigned to the dynamics of the molecules in the surface layer. The temperature dependence of its characteristic frequencies obeys the Vogel-Fulcher-Tammann law, which is found to be typical for glass-forming liquids. The quasi two-dimensional character of the glass transition in the surface layer is discussed for the first time. At the nematic-to-isotropic transition temperature of the bulk, the composites show a continuous decrease of the characteristic frequencies as a function of the alkyl chain length, while the bulk LCs show the well known odd-even behaviour. The magnitude and temperature dependence of the slow relaxation process in the composites (molecules on an outer surface) agree with those of the same molecules confined to the nanopores of molecular sieves (internal surface).     

Determination of formic and acetic acids in air by piezoelectric microweighing

The quantitative and kinetic parameters of sorption of formic and acetic acids on thin films of various modifiers of piezoelectric quartz resonator electrodes are determined. Parameters of film formation on the electrodes (application procedure and thickness) are optimized. Methods for joint and separate determination of formic and acetic acids in air by piezoelectric microweighing with single- and double-sensor devices are developed.     

High pressure elastic and plastic deformations of silica: In situ diamond anvil cell Raman experiments

Normal silica glass is usually referred to as low density amorphous silica as it can be converted to high density amorphous silica by a hydrostatic pressure (polyamorphic transition). In this work in situ Raman experiments are performed in a diamond anvil cell up to 18 GPa. The pressure effects on the structure of silica after successive compression decompression experiments are analyzed. The mode Grüneisen parameters corresponding to the elastic compression of high density amorphous silica are obtained and compared with those of normal silica. A reorganization of the high density amorphous silica below 3 GPa is evidenced.     

MgO films grown on yttria-stabilized zirconia by molecular beam epitaxy

MgO films were grown on (0 0 1) yttria-stabilized zirconia (YSZ) substrates by molecular beam epitaxy (MBE). The crystalline structures of these films were investigated using X-ray diffraction and transmission electron microscopy. Growth temperature was varied from 350 to 550 °C, with crystalline quality being improved at higher temperatures. The MgO films had a domain structure: (1 1 1)[1 1 2¯]_MgO(0 0 1)[1 0 0]_YSZ with four twin variants related by a 90° in-plane rotation about the [1 1 1]_MgO axis. The observed epitaxial orientation was compared to previous reports of films grown by pulsed laser deposition and sputtering and explained as resulting in the lowest interface energy.     

Predicting the onset of DNA supercoiling using a non-linear hemitropic elastic rod

Elastic rod models provide a means to interpret single molecule DNA experiments as well as predict DNA behavior under physiological conditions. Here we use an elastic rod model to predict the stability boundary (critical torque vs. applied tension) for single molecule DNA experiments in which the molecule is subjected to applied tension and twist. We discuss the shortcomings of the usual isotropic rod model. We then derive a consistent non-linear material law from the general representation for a hemitropic (chiral) rod. Finally, we present results of a standard bifurcation analysis predicting the stability boundary. We find results from the non-linear hemitropic rod to match the data closely.     

Geometry and electronic structure of a heterometallic cluster Mo<Subscript>2</Subscript>Mg<Subscript>2</Subscript> in different oxidation states of Mo: a DFT study

Reduction of tetranuclear heterometallic complex Mo₂Mg₂ was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex [Mo^VIO₂Mg(MeOH)₂(OMe)₄]₂ and a partially reduced Mo^V complex are in good agreement with experimental data. The reduced Mo^III complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with release of a coordination position at the Mo atoms requires small energy expenditure. One can assume that the reduction of the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–457, March, 2008.