Effect of the Pauli exclusion principle and the polarization of nuclei on the potential of their interaction for the example of the 16O+16O system

On the basis of the energy-density method, the effect of simultaneously taking into account the Pauli exclusion principle and the monopole and quadrupole polarizations of interacting nuclei on their interaction potential is considered for the example of the ¹⁶O + ¹⁶O system by using the wave function for the two-center shell model. The calculations performed in the adiabatic approximation reveal that the inclusion of the Pauli exclusion principle and the polarization of interacting nuclei, especially their quadrupole polarization, has a substantial effect on the potential of the nucleus-nucleus interaction.     

Synthesis of optically active hydroxyphosphonates

The reduction of dimenthyl ketophosphonates with sodium borohydride involves asymmetric induction at the α‐carbon atom, resulting in a small excess of the (R)‐enantiomer of the α‐hydroxyphosphonate formed. A higher ee purity was achieved if the reduction of chiral dimenthyl ketophosphonates was carried out by the chiral complex of NaBH₄‐L ‐proline, owing to the double asymmetric induction at the α‐carbon atom. The hydroxyphosphonates obtained were isolated in a diastereomerically pure state and were transformed to the optically active, free hydroxyalkylphosphonic acids. The (R)‐configuration of one of them was proved by X‐ray crystal structure analysis. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:133–139, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20391     

Simulations of Microbial-Enhanced Oil Recovery: Adsorption and Filtration

In the context of microbial-enhanced oil recovery (MEOR) with injection of surfactant-producing bacteria into the reservoir, different types of bacteria attachment and growth scenarios are studied using a 1D simulator. The irreversible bacteria attachment due to filtration similar to the deep bed filtration (DBF) is examined along with the commonly used reversible equilibrium adsorption (REA). The characteristics of the two models are highlighted. The options for bacteria growth are the uniform growth in both phases and growth of attached bacteria only. It is found that uniform growth scenario applied to filtration model provides formation of two oil banks during recovery. This feature is not reproduced by application of REA model or DBF with growth in attached phase. This makes it possible to select a right model based on the qualitative analysis of the experimental data. A criterion is introduced to study the process efficiency: the dimensionless time at which average recovery between pure water injection and maximum surfactant effect is reached. This characteristic recovery period (CRP) was studied as a function of the different MEOR parameters such as bacterial activity, filtration coefficients, and substrate injection concentrations. For both growth scenarios, there is a zone of optimal activity at which the CRP is minimal. Dependence of the CRP on substrate concentration for uniform growth scenario has also an optimal zone. Therefore, growth rate and the substrate concentration should be above a certain threshold value and still not be too high to obtain the minimum CRP. On the other hand, no such zone was found if the bacteria could grow only in the attached phase. Dependencies on both the injected concentration and filtration coefficient are monotonous in this case.     

Rates of superlinear convergence for classical quasi-Newton methods

Mathematical Programming - We study the local convergence of classical quasi-Newton methods for nonlinear optimization. Although it was well established a long time ago that asymptotically these...     

Use of Chelate Complexes of Lead(II) in Low-Temperature Technologies of Ceramic Piezoelectric Materials

Technology is suggested for fabrication of ceramic piezoelectric materials from the lead-containing ferroelectric phase. The technology includes a low-temperature synthesis of ultradispersed lead titanate and zirconate powders and also of phases of solid solutions on their basis and the low-temperature procedure for sintering of ceramic fabricated from ultradispersed powders of ferroelectric phases. As precursors used in the suggested low-temperature synthesis serve lead glycerate and tartrate. It was found that, when interacting (at temperatures of 240–330°C) with hydroxo-peroxo-aqua complexes of titanium and(or) zirconium(IV) in the course of 30–40 min, the precursors form ultradispersed powders of these phases, which are single-phase and contain particles with average size of less than 100 nm. It was shown that using the suggested technology makes it possible not only to reduce the energy expenditure for separate procedures for synthesis of ultradispersed ferroelectric phases and for synthesis of piezoelectric materials, but also to substantially diminish the discharge of lead(II) compounds into the atmosphere of industrial premises. It was also shown that the technology enables fabrication of piezoelectric materials with prescribed values of electrical parameters.

     

Distribution of benzo-substituted crown-ethers between chloroform and water: effects of macrocycle ring size and lithium chloride

Small size benzo-substituted crown ethers are attractive complexing agents for lithium isotope separation by solvent extraction. Low transfer of the crown ethers from solvent to water is a key point for applicability of the extractants. In the present study, 9- and 12-membered crown ethers were synthesized, and their distribution between chloroform and water was studied. Polyether ring size, benzene substituents and addition of LiCl to water were found to effect on distribution constants. Low losses of the macrocycles were observed at single-stage contact with aqueous phase. However, these losses should be taken into account in the design of multistage processes for the preparation of highly enriched lithium isotopes.     

Chemosensory performance of molecularly imprinted fluorescent conjugated polymer materials

Fluorescent conjugated polymers are an attractive basis for the design of low detection limit sensing devices owing to their intrinsic signal amplification capability. A simple and universal method to rationally control or fine-tune the chemodetection selectivity of conjugated polymer materials toward a desired analytical target would further benefit their applications. In a quest of such a method we investigated a general approach to cross-linked molecularly imprinted fluorescent conjugated polymer (MICP) materials that possess an intrinsic capability for signal transduction and have potential to enhance selectivity and sensitivity of sensor devices based on conjugated polymers. To study these capabilities, we prepared an MICP material for the detection of 2,4,6-trinitrotoluene and related nitroaromatic compounds. We found the imprinting effect in this material to be based on analyte shape/size recognition being substantial and generally overcoming other competing thermodynamically determined trends. The described molecularly imprinted fluorescent conjugated polymers show remarkable air stability and photostability, high fluorescence quantum yield, and reversible analyte binding and therefore are advantageous for sensing applications due to the ability to "preprogram" their detection selectivity through a choice of an imprinted template.     

An optimum Hamiltonian for non-Hermitian quantum evolution and the complex Bloch sphere

For a quantum system governed by a non-Hermitian Hamiltonian, we studied the problem of obtaining an optimum Hamiltonian that generates nonunitary transformations of a given initial state into a certain final state in the smallest time τ. The analysis is based on the relationship between the states of the two-dimensional subspace of the Hilbert space spanned by the initial and final states and the points of the two-dimensional complex Bloch sphere.     

3,5‐Bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐piperidone and 3,5‐bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐oxopiperidinium chloride: potential biophotonic materials

In the title compound 3,5‐bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐piperidone, C₂₂H₂₃NO₃, (I), the central heterocyclic ring adopts a flattened boat conformation, while in the related salt 3,5‐bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐oxopiperidin­ium chloride, C₂₂H₂₄NO₃⁺·Cl⁻, (II), the ring exhibits a `sofa' conformation in which the N atom deviates from the planar fragment. The pendant benzene rings are twisted from the heterocyclic ring planes in both mol­ecules in the same direction, the range of dihedral angles between the ring planes being 24.5 (2)–32.7 (2)°. The dominant packing motif in (I) involves centrosymmetric dimers bound by weak intermolecular C—H⋯O hydrogen bonds. In (II), cations and anions are linked by strong N—H⋯Cl hydrogen bonds, while weak C—H⋯O and C—H⋯Cl hydrogen bonds link the cations and anions into a three‐dimensional framework.