Triruthenium dodecacarbonyl/triphenylphosphine catalyzed dehydrogenation of primary and secondary alcohols

Dehydrogenation of alcohols into aldehydes and ketones by Ru₃(CO)₁₂/PPh₃ based homogeneous catalysis has been investigated as an alternative for the classical Oppenauer oxidation. Several catalytic systems have been screened in the Oppenauer-like oxidation of alcohols. A systematic study of various combinations of Ru₃(CO)₁₂, mono- and bidentate ligands and hydride acceptors was performed to enable dehydrogenation of primary alcohols to stop at the aldehyde stage. Among many H-acceptors screened, diphenylacetylene (tolane) proved the most suitable judged from its smooth reduction. Electron rich and deficient analogues of tolane have been synthesized and, based on competition experiments between these H-acceptors, a tentative catalytic cycle for the Ru₃(CO)₁₂/PPh₃-catalyzed dehydrogenations has been proposed.     

Structure and catalytic activity of some soluble polyethylene glycol-peptide conjugates

Soluble catalysts for the Juliá-Colonna asymmetric epoxidation reaction have been constructed in three different ways, using NH₂-PEG-OMe as the support system: suitable solvents have been identified and it is shown that the degree of helicity of the conjugates correlates with the extent of conversion and (to a lesser extent) the enantioselectivity of epoxidation.     

Dynamic stability of weakly damped oscillators with elastic impacts and wear

The dynamics of non-linear oscillators comprising of a single-degree-of-freedom system and beams with elastic two-sided amplitude constraints subject to harmonic loads is analyzed. The beams are clamped at one end, and constrained against unilateral contact sites near the other end. The structures are modelled by a Bernoulli-type beam supported by springs using the finite element method. Rayleigh damping is assumed. Symmetric and elastic double-impact motions, both harmonic and sub-harmonic, are studied by way of a Poincaré mapping that relates the states at subsequent impacts. Stability and bifurcation analyses are performed for these motions, and domains of instability are delineated. Impact work rate, which is the rate of energy dissipation to the impacting surfaces, is evaluated and discussed. In addition, an experiment conducted by Moon and Shaw on the vibration of a cantilevered beam with one-sided amplitude constraining stop is modelled. Bifurcation observed in the experiment could be captured.     

Characterization of oxide layers on amorphous Mg-based alloys by Auger electron spectroscopy with sputter depth profiling

Amorphous ribbons of Mg-Y-TM-[Ag] (TM: Cu, Ni), prepared by melt spinning, were subjected to electrochemical investigations. Oxide layers formed anodically under potentiostatic control in different electrolytes were investigated by AES and sputter depth profiling. Problems and specific features of characterization of the composition of oxide layers and amorphous ternary or quaternary Mg-based alloys have been investigated. In the alloys the Mg(KL(23)L(23)) peak exhibits a different shape compared to that in the pure element. Analysis of the peak of elastically scattered electrons proved the absence of plasmon loss features, characteristic of pure Mg, in the alloy. A different loss feature emerges in Mg(KL(23)L(23)) and Cu(L(23)VV). The system Mg-Y-TM-[Ag] suffers preferential sputtering. Depletion of Mg and enrichment of TM and Y are found. This is attributed mainly to the preferential sputtering of Mg. Thickness and composition of the formed oxide layer depend on the electrochemical treatment. After removing the oxide by sputtering the concentration of the underlying alloy was found to be affected by the treatment.     

Recognition of subgroups of direct products of hyperbolic groups

We give examples of direct products of three hyperbolic groups in which there cannot exist an algorithm to decide which finitely presented subgroups are isomorphic.

     

Study of ferroelectric switching by domain-wall induced light scattering

Measurements of 90°-scattering of weak laser light are used to investigate pulsed domain switching in ferroelectrics. The studies were performed on strontium-barium niobate (SBN) single crystals. A good agreement of the switching parameters estimated from the optical measurements with those obtained by means of conventional electrical methods proves the validity of the optical method for switching studies. Due to the limited scattering volume in all three spatial dimensions, the method facilitates local probing of the switching within the crystal bulk. In particular, local specialities of the domain density can be detected. Furthermore, the excellent time resolution inherent in optical probing techniques allows for a comprehensive study of the dynamics.     

Substantiation of the two-temperature kinetic model by comparing calculations within the kinetic and fluid models of the positive column plasma of a dc oxygen discharge

Results from kinetic and fluid simulations of the positive column plasma of a dc oxygen discharge are compared using commercial CFDRC software (), which enables one to perform numerical simulations in an arbitrary 3D geometry with the use of both the fluid equations for all the components (fluid model) and the kinetic equation for the electron energy distribution function (kinetic model). It is shown that, for both the local and nonlocal regimes of the formation of the electron energy distribution function (EEDF), the non-Maxwellian EEDF can satisfactorily be approximated by two groups of electrons. This allows one to take into account kinetic effects within the conventional fluid model in the simplest way by using the proposed two-temperature approximation of the nonequilibrium and nonlocal EEDF (2T fluid model).     

Photostimulated phenomena in relaxors

The action of illumination on the conducting and dielectric properties of lead magnoniobate was investigated. The photostimulated currents were examined and the spectral dependence of photoconductivity in the region of diffuse phase transition was obtained. It was found that the illumination affects the dielectric properties and that its action is memorized at temperatures below room temperature. The role of defect states in the formation of relaxor properties is discussed on the basis of the obtained data.     

Role of vitreous matrix on the optical activity of Ge-doped silica

We report an experimental study on the relationship between the optical activity of Ge-oxygen deficient centers and dynamic properties and conformational heterogeneity of vitreous matrix in silica. We focus our attention on the absorption band at ∼5.2 eV (B_2β) and on the two related emissions at ∼4.2 eV (α_E) and at ∼3.1 eV (β). From the temperature dependence of B_2β band we estimate a mean energy value of 26 meV for local vibrational modes coupled to the electronic transition, suggesting that the chromophore and its surrounding have access to low frequency dynamics. From the thermal behavior of the two emissions we distinguish the two competitive relaxation processes from the first singlet excited state S₁: the radiative one, giving rise the α_E band, and the thermally activated intersystem-crossing process between S₁ and the triplet state T₁, originating the β band. The intersystem-crossing rate increases on increasing the temperature, determining an opposite thermal behavior of the intensity of the two emissions. However, this temperature dependence cannot be rationalized by a simple Arrhenius law and the α_E decay kinetics at high temperatures do not follow a single exponential law, suggesting a complex landscape of configurational energies of the process.