Crystal growth of PbTe and (Pb,Sn)Te by the bridgman method and by THM

Synthesis and growth of PbTe and (Pb, Sn)Te single crystals by the Bridgman method and by the Travelling Heater Method (THM) from Te-rich solutions are described. It is to be seen from comparative investigations that seeded THM growth reproducibly provides oriented single-crystalline ingots free of low-angle grain boundaries and with etch pit densities of 8–12 × 10⁴ cm⁻². All the materials were p-type with carrier concentrations from 1 to 2 × 10¹⁸ cm⁻³.     

Invariants Cohomologiques de Rost En Caractéristique PositiveRost''s Cohomological Invariants in Positive Characteristic

Let G/F be a semisimple algebraic group defined over a field F with characteristic . Let us denote by the Galois cohomology group introduced by Kato. If , we show that the p-primary part of Rost's invariant lifts in characteristic 0. This result allows to deduce properties of the Rost invariant in positive characteristic from known properties in characteristic 0. The case of Merkurjev–Suslin's invariant is specially interesting, i.e. if G/F=SL(D) for a central simple algebra D/F with degree p and class , one has and an element is a reduced norm if and only if the cup-product is trivial in ; one characterizes also in positive characteristic fields with p-dimension by the surjectivity of reduced norms.In a second part, we study Rost invariants when the base field is complete for a discrete valuation. As planned by Serre, invariants are then linked with Bruhat–Tits' theory, this yields a new proof of their nontriviality.     

On the dimers of β-tocopherol

Upon oxidation in aprotic media, β-tocopherol (2) forms a spiro-dimer (10) as the main product. The reaction mechanism is a hetero-Diels-Alder process with inverse electron demand of two intermediate ortho-quinone methide molecules. The spiro-dimer can be reduced to the corresponding symmetric ethano-dimer (11). In contrast to the well-studied α-tocopherol case, spiro-dimer and ethano-dimer do not form a reversible redox pair, their interconversion is accompanied by coupling reactions at C-7 with 7a-(β-tocopher-5a-yl)-β-tocopherol (13) as the main byproduct besides some oligomeric material. The full NMR assignments (¹H, ¹³C) of the β-tocopherol oxidation products are given.     

Antioxidant properties of natural and synthetic chromanol derivatives: study by fast kinetics and electron spin resonance spectroscopy

[structure: see text] Chromanol-type compounds act as antioxidants in biological systems by reduction of oxygen-centered radicals. Their efficiency is determined by the reaction rate constants for the primary antioxidative reaction as well as for disproportionation and recycling reactions of the antioxidant-derived radicals. We studied the reaction kinetics of three novel chromanols: cis- and trans-oxachromanol and the dimeric twin-chromanol, as well as ubichromanol and ubichromenol, in comparison to alpha-tocopherol and pentamethylchromanol. The antioxidant-derived radicals were identified by optical and electron spin resonance spectroscopy (ESR). The kinetics of the primary antioxidative reaction and the disproportionation of the chromanoxyl radicals were assessed by stopped-flow photometry in different organic solvents to simulate the different polarities associated with biomembranes. Furthermore, the reduction of the chromanoxyl radicals by ubiquinol and ascorbate was measured after laser-induced one-electron chromanol oxidation in ethanol and in a micellar system, respectively. The rate constants showed that twin-chromanol had better radical scavenging properties than alpha-tocopherol and a significantly slower disproportionation rate of its corresponding chromanoxyl radical. In addition, the radical derived from twin-chromanol is reduced by ubiquinol and ascorbate at a faster rate than the tocopheroxyl radical. Finally, twin-chromanol can deliver twice as many reducing equivalents, which makes this compound a promising new candidate as artificial antioxidant in biological systems.     

Kinetic anomalies of mixed crystal growth and their effect on the crystal isomorphic composition

Growth rate anomalies in aqueous solution growth of NaClO₃ and KClO₃ were first revealed by V. V. Sipyagin in 1967 and attributed to “kinetic anomalies”. These phenomena were confirmed in a series of other studies and for a variety of substances. Therefore, some universality of these anomalies was supposed that should be due to structural transformations in the liquid solutions. In this paper, we present for the first time results on growth rate oscillations found in mixed crystal growth and their impact on the isomorphic composition of solid solutions. Thick (100) Na(Cl,Br)O₃ layers were grown at fixed supercooling conditions onto NaClO₃ seeds in a microcrystallization cell equipped with an optical microscope. In the temperature range of 33 – 41 °C, four kinetic anomalies were found in solutions of a chlorate: bromate molar ratio of 20: 1 at supercoolings of 2.0 K and 3.0 K. Lattice parameter measurements of the grown Na(Cl,Br)O₃ layers revealed a linear dependence of lattice constant vs. growth rate. By measuring Vegard's law (lattice parameter vs. solid solution composition) we were able to determine the oscillations in mixed crystal composition that accompany the kinetic anomalies in solid solution systems. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Rate constants of the thermal cis‐trans isomerization of azobenzene dyes in solvents,acetone/water mixtures,and in microheterogeneous surfactant solutions

Rate constants k_iso of the thermal cis‐trans isomerization of four 4,4’‐nitro‐aminoazobenzenes with different amino groups have been determined in homogeneous aprotic solvents and polyglykol oligomers, primarily by means of conventional flash photolysis. The rate constants have been correlated with polarity (according to λ_max from UV/Vis absorption spectra of the trans isomers) and bulk viscosity of the solvents. Qualitative conclusions about the influence of varying concentrations of water with respect to polarity and hydrogen bonding on k_iso‐ and λ_max‐values in acetone/water mixtures were derived. Based on these results the data from microheterogeneous solutions have been interpreted. In microheterogeneous water/surfactant solutions k_iso‐values of selected azo dyes were strongly dependent on the concentrations of SDS, Triton^®X‐100, C₁₂EO₈ in water, and varied with the composition of bicontinuous microemulsions of Igepal^® CA‐520/ heptane/water. The large spread of isomerization rate constants is in part due to varying microviscosity. Replacement of H₂O by D₂O in aqueous surfactant solutions produced surprisingly large kinetic solvent isotope effects. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 337–350, 1999     

Comparaison entre les solutions solides PLZT et les materiaux PZT bisubstitues

A systematic study of PLZT materials with composition close to the rhombohedral-tetragonal phase transition boundary at room temperature showed that piezoelectric properties of such materials are comparable with those exhibited by PZT with similar composition but containing two substituents. The best results were obtained with 6% lanthanum and 58% zirconium samples.     

Molecular Dissociation on the SiC(0001) 3×3 Surface

In the framework of density functional theory, the adsorption of the halogenated polycyclic aromatic hydrocarbon 2,11‐diiodohexabenzocoronene (HBC‐I₂) on the SiC(0001) 3×3 surface has been investigated. Nondissociative and dissociative molecular adsorption is considered, and simulated scanning tunneling microscopy (STM) images are compared with the corresponding experimental observations. Calculations show that dissociative adsorption is favorable and reveal the crucial importance of the extended flat carbon core on molecule–surface interactions in dissociative adsorption; the iodine atom–surface interaction is of minor importance. Indeed, removing iodine atoms does not significantly affect the STM images of the central part of the molecule. This study shows that the dissociation of large halogenated polycyclic aromatic hydrocarbon molecules can occur on the SiC surface. This opens up interesting perspectives in the chemical reactivity and functionalization of wide band gap semiconductors.     

Equivariant pretheories and invariants of torsors

In the present paper we introduce and study the notion of an equivariant pretheory (basic examples are equivariant Chow groups of Edidin and Graham, Thomason??s equivariant K-theory and equivariant algebraic cobordism). Using the language of equivariant pretheories we generalize the theorem of Karpenko and Merkurjev on G-torsors and rational cycles. As an application, to every G-torsor E and a G-equivariant pretheory we associate a ring which serves as an invariant of E. In the case of Chow groups this ring encodes the information about the motivic J-invariant of E, in the case of Grothendieck??s K ₀ indexes of the respective Tits algebras and in the case of algebraic cobordism ?? it gives a quotient of the cobordism ring of G.     

The Rost nilpotence theorem for geometrically rational surfaces

We show that the Rost nilpotence theorem is true for geometrically rational surfaces over fields of characteristic zero.