Sterically Active Electron Pairs in Lead Sulfide? An Investigation of the Electronic and Vibrational Properties of PbS in the Transition Region Between the Rock Salt and the α‐GeTe‐Type Modifications

Recently, we have investigated the energy landscape of PbS for many different pressures on the ab initio level by using Hartree–Fock and density functional theory to globally search for possible thermodynamically stable and metastable structures. The perhaps most fascinating observation was that besides the experimentally known modification exhibiting the rock salt structure a second minimum exists close‐by on the landscape showing the low‐temperature α‐GeTe‐type structure. In the present study, we investigate the possible reasons for the existence of this metastable modification; in particular we address the question, whether the α‐GeTe‐type modification might be stabilized (and conversely the rock salt modification destabilized) by steric effects of the non‐bonding electron pair.     

Time-dependent fluctuations and particle production in cosmological de Sitter and anti-de Sitter spaces

We study the evolution of time-dependent fluctuations and particle production in an expanding dS and contracting AdS universe. Using the functional Schrödinger formalism we are able to probe the time-dependent regime which is out of the reach of the standard approximations like the Bogolyubov method. In both cases, the evolution of fluctuations is governed by the harmonic oscillator equation with time-dependent frequency. In the case of an expanding dS universe we explicitly show that the frequency of fluctuations produced at a certain moment diminish in time, while the distribution of the created particles quickly approaches the thermal radiation of the dS space. In the case of a contracting AdS universe we show that the frequency of fluctuations produced at a certain moment grow in time. Nominally, the temperature of radiation diverges as the Big Crunch is approaching, however, increasing oscillations of the spectrum make the temperature poorly defined, which is in agreement with the fact that AdS space does not have an event horizon which would cause thermal radiation. Unlimited growth of fluctuations indicates that an eventual tunneling into AdS vacuum would have catastrophic consequences for our universe.     

Can primordial magnetic fields seeded by electroweak strings cause an alignment of quasar axes on cosmological scales?

The decay of nontopological electroweak strings may leave an observable imprint in the Universe today in the form of primordial magnetic fields. Protogalaxies preferentially tend to form with their axis of rotation parallel to an external magnetic field, and, moreover, an external magnetic field produces torque which tends to align the galaxy axis with the magnetic field. We demonstrate that the shape of a magnetic field left over from two looped electroweak strings can explain the observed nontrivial alignment of quasar polarization vectors and make predictions for future observations.     

Aryl acrylate based high‐internal‐phase emulsions as precursors for reactive monolithic polymer supports

Water‐in‐oil high‐internal‐phase emulsions (HIPEs), containing 4‐nitrophenyl acrylate and 2,4,6‐trichlorophenyl acrylate as reactive monomers, were prepared and polymerized, and highly porous monolithic materials resulted. The novel materials were studied by combustion analysis, Fourier transform infrared spectroscopy scanning electron microscopy, mercury porosimetry, and N₂ adsorption/desorption analysis. With both esters, cellular macroporous monolithic polymers were obtained; the use of 4‐nitrophenyl acrylate resulted in a cellular material with void diameters between 3 and 7 μm and approximately 3‐μm interconnects, whereas the use of 2,4,6‐trichlorophenyl acrylate yielded a foam with void diameters between 2 and 5 μm, most interconnects being around 1 μm. The resulting monoliths proved to be very reactive toward nucleophiles, and possibilities of functionalizing the novel polymer supports were demonstrated via reactions with amines bearing additional functional groups and via the synthesis of an acid chloride derivative. Tris(hydroxymethyl)aminomethane and tris(2‐aminoethyl)amine derivatives were obtained. The hydrolysis of 4‐nitrophenylacrylate removed the nitrophenyl group, yielding a monolithic acrylic acid polymer. Furthermore, functionalization to immobilized acid chloride was performed very efficiently, with more than 95% of the acid groups reacting. The measurement of the nitrogen content in 4‐nitrophenyl acrylate poly(HIPE)s after various times of hydrolysis showed the influence of the total pore volume of the monolithic polymers on the velocity of the reaction, which was faster with the more porous polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 296–303, 2005     

Synthesis of Aliphatic Esters of Cinnamic Acid as Potential Lipophilic Antioxidants Catalyzed by Lipase B from Candida antarctica

Immobilized lipase from Candida antarctica (Novozyme 435) was tested for the synthesis of various phenolic acid esters (ethyl and n-butyl cinnamate, ethyl p-coumarate and n-butyl p-methoxycinnamate). The second-order kinetic model was used to mathematically describe the reaction kinetics and to compare present processes quantitatively. It was found that the model agreed well with the experimental data. Further, the effect of alcohol type on the esterification of cinnamic acid was investigated. The immobilized lipase showed more ability to catalyze the synthesis of butyl cinnamate. Therefore, the process was optimized for the synthesis of butyl cinnamate as a function of solvent polarity (logP) and amount of biocatalyst. The highest ester yield of 60.7 % was obtained for the highest enzyme concentration tested (3 % w/w), but the productivity was for 34 % lower than the corresponding value obtained for the enzyme concentration of 1 % (w/w). The synthesized esters were purified, identified, and screened for antioxidant activities. Both DPPH assay and cyclic voltammetry measurement have shown that cinnamic acid esters have better antioxidant properties than cinnamic acid itself.     

Two-phase flows in gun barrel: Theoretical and experimental studies

In the paper theoretical and numerical model of two-phase flow of solid granular propellant and its products of combustion in the gun barrel during interior ballistic cycle is given. Two cases are considered: base ignition of propellant charge and ignition by igniter. The theoretical model includes the balance equations of mass, momentum and energy for both phases, as well as necessary constitutive laws. The igniter efflux in the propellant chamber is obtained by incorporation in the model the two-phase flow model of igniter function. The convergent, unconditionally stable, numerical procedure is formed to solve the system of equations of the theoretical model. An original procedure of numerical grid adaptation to the flow field increase, caused by the projectile motion down the gun bore, is developed. The TWOPIB code for the computation of whole interior ballistic cycle of ammunition is developed. Four kinds of experimental investigations were carried out:igniter function in open air, flamespreading through propellant charge in the fibreglass tube during base ignition or during ignition by igniter, and firing of 100 mm APFSDS projectile. Verification of the theoretical–numerical approach by the comparison with experimental data is carried out. The great number of computational results is presented for the parameters that can not be measured, but which are necessary for more complete understanding of examined processes. The presented theoretical–numerical access enables, not only the complete optimisation of propellant charges, but more successful solutions of many interior ballistic problems.