Raman study of TiO2 role in SiO2-Al2O3-MgO-TiO2-ZnO glass crystallization

Tough glass-ceramic material of special mechanical properties with nanosize crystal phases formed by appropriately controlled crystallization was studied by Raman spectroscopy. It was obtained by TiO2 activated crystallization of Mg-aluminosilicate glass of SiO2-Al2O3-MgO-TiO2-ZnO composition. Crystallization was preceded by a change in the TiO2 structural position and state, which is manifested by a changed color of glass from yellow into blue shortly before the glass transformation (Tg) temperature. Raman spectroscopy was applied to explain the mechanism of this process and to establish the role of TiO2 in the early stage of glass crystallization that precedes a complete crystal phase formation. The starting glasses were found in almost complete disorder, since all bands were weak, broad and dominated by a Bose band at about 90 cm-1. After the sample annealing all bands turned out better resolved and the Bose band practically disappeared, both confirming the amorphous structure reorganization process. A multiplet observed in the vicinity of 150 cm-1 we assigned to the anatase and other titania structures that can be considered prime centers of crystallization. Finally, in the closest neighborhood of the Rayleigh line the low frequency mode characterizing nanoparticles was observed. According to this band theory, the mean size of initial titania crystallites is about 10nm for all samples, but the size distribution varies within factor two among them.     

The existence of global in space variables solution for non-linear subelliptic equation of floating water

The existence of global in space variables solutions for a class of non-linear subelliptic evolution operators is proved. A Cauchy problem and an initial-boundary value problem are considered using the contraction theorem and Galerkin methods.     

5,7,12,14-Tetramethyldimethoxybenzo[b,i][1,4,8,11]tetraazacyclodecine,a new tumoricidal pseudo-porphyrin

The title compound, a mixture of two isomers differing in the position of a methoxy substituent in one benzene ring, was obtained in a Ni-templated synthesis directly as a water soluble dihydrochloride of the free base. The cyclic voltametry study indicated that in a neutral solution the reduction and oxidation are irreversible one electron processes, the latter leading to cation radical undergoing polymerization, a process followed by deposition of a film on the electrode. In 1,2-dichloroethane the cation radical is oxidized to a dication, both species being much less stable than those originating from meso-tetraphenylporphyrin. The title compoud at 2.5 × 10^?5 M in Tris buffer showed a 50% inhibition of the growth of malignant melanoma cells as compared to a 44% inhibition shown by a water soluble meso-monomethoxy-tris(N-methylpyridinium)porphyrin. The exposure to light for 30 minutes at 2.5 times smaller concentration increased the inhibition caused by the pseudo-porphyrin from 9% to 49%.     

Gravitational Aharonov-Bohm Effect

We study a purely gravitational Aharonov-Bohm effect. The space-time curvature is concentrated in the quasiregular singularity of a cosmic string, outside of which space-time is (locally) flat. The symmetries of this field configuration are described by the groupoid symmetries rather than by the usual group symmetries. The groupoid in question is formed by homotopy classes of piecewise smooth paths in the cosmic string region. A gravitational counterpart of the Aharonov-Bohm effect occurs if the symmetry of the system, with respect to the groupoid action, is broken down.     

X-ray structure of isomeric 3-chloro-4-(methylthio)- and 4-chloro-3-(methylthio)quinolines

The crystal and molecular structures of two isomeric 3,4- and 4,3-chloro-(methylthio)quinolines have been determined. For 3-chloro-4-(methylthio)-quinoline (3-Cl–4-MeS–Q); triclinic, space group ,a=7.199(3),b=7.919(3),c=8.921(3) Å, =89.74(3), =74.29(3), =78.55(3)°. For 4-chloro-3-(methylthio)quinoline (4-Cl–3-MeS–Q): monoclinic, space group P2₁/n,a=12.860(4),b=5.424(2),c=13.434(4) Å, =90.84(3)°. The values of the Cl...S distance as well as those for the Cl–C–C(S) and (Cl)C–C–S angles indicate the attractive interaction between ortho-situated heteroatoms in isomer 4-Cl–3-MeS–Q contrary to the effects observed in the case of 3-Cl–4-MeS–Q. The conclusions were confirmed by calculations of atomic charges withab initio method 4-31G basis set, which show positively charged sulfur atom in 4-Cl–3-MeS–Q and negatively charged sulfur in 3-Cl–4-MeS–Q.Part XXX in the series of Azinyl Sulfides.     

First-principles study of fluoroform adsorption on a hexagonal ice (0001) surface: weak hydrogen bonds-strong structural effects

For isolated fluoroform (F(3)CH) molecules adsorbed on a hexagonal ice (0001) surface the properties of blue- and red-shifting hydrogen bonds were studied using static density functional theory (DFT) calculations and Car-Parrinello molecular dynamics (CP-MD) simulations. A systematic search by starting from many initial configurations was performed to determine the lowest-energy structures of F(3)CH on the ice surface, and for the optimized geometries the vibrational frequencies were calculated. The local minima structures are analyzed in terms of their coordination to the surface, with special focus on identifying blue-shifting hydrogen bonds via their spectroscopic signature of an increased frequency of the C-H fundamental stretching vibration. Subsequently, by CP-MD simulations the stability of the lowest-energy configurations at finite temperatures was verified and possible transformation pathways connecting the local minima structures were explored.     

Existence of solutions for hyperbolic hemivariational inequalities

In this paper we study a hyperbolic hemivariational inequality with a nonlinear, pseudomonotone operator depending on the derivative of an unknown function and a linear, monotone operator depending on an unknown function. Using the surjectivity result for L-pseudomonotone operators, an existence result for such inequalities is proved.     

Ab initio calculations of the vibrational force field and IR intensities of the ammonia dimers

Ab initio SCF calculations using the 4-31G basis set have been carried out to determine the equilibrium geometry, force constants and dipole moment derivatives of the linear (C_s and cylic (C_2h) ammonia dimers. The results are compared with monomer calculations and experimental data.