Synthesis and cation complexation of calix[4]azacrowns and a spirobiscalix[4]azacrown

The synthesis and complexation properties of three new derivatives, one spirobiscalix[4]azacrown (1) and two calix[4]azacrown (2 and 3), are reported. Complexation studies of the three ligands toward transition and heavy metal cations have been carried out and monitored by UV absorption spectrophotometry in acetonitrile. Mononuclear complexes were detected for all complexes, whereas binuclear species (M₂L) were also formed in the case of ligand 1 with Cu²⁺ and Pb²⁺. The extraction properties of 1, 2 and 3 toward Cu²⁺, Zn²⁺, Pb²⁺, Ag²⁺ and Cd²⁺ are also reported. The results showed that complexation is the main factor affecting extraction with ligands 2 and 3, while with ligand 1 it is not.     

Reprint of: Extraction of fluoxetine from aquatic and urine samples using sodium dodecyl sulfate-coated iron oxide magnetic nanoparticles followed by spectrofluorimetric determination

A new method based on the combination of magnetic solid phase extraction (MSPE) and spectrofluorimetric determination was developed for isolation and preconcentration of fluoxetine form aquatic and biological samples using sodium dodecyl sulfate (SDS) coated Fe₃O₄ nanoparticles (NPs) as a sorbent. The unique properties of Fe₃O₄ NPs including high surface area and strong magnetism were utilized effectively in the MSPE process. Effect of different parameters influencing the extraction efficiency of fluoxetine including the amount of Fe₃O₄ and SDS, pH value, sample volume, extraction time, desorption solvent and time were optimized. Under optimized condition, the method was successfully applied to the extraction of fluoxetine from water and urine samples and absolute recovery amount of 85%, detection limit of 20 μg L⁻¹ and a relative standard deviation (RSD) of 1.4% were obtained. The method linear response was over a range of 50–1000 μg L⁻¹ with R² = 0.9968. The relative recovery in different aquatic and urine matrices were investigated and values of 80% to 104% were obtained. The whole procedure showed to be conveniently fast, efficient and economical for extraction of fluoxetine from environmental and biological samples.     

On a new Kato class and positive solutions of Dirichlet problems for the fractional Laplacian in bounded domains

The purpose of this paper is to extend some results of the potential theory of an elliptic operator to the fractional Laplacian (−Δ)^α/2, 0<α<2, in a bounded C^1,1 domain D in Rⁿ. In particular, we introduce a new Kato class K_α(D) and we exploit the properties of this class to study the existence of positive solutions of some Dirichlet problems for the fractional Laplacian.     

Attractor States and Quantum Instabilities in de Sitter Space

The asymptotic behavior of the energy–momentum tensor for a free quantized scalar field with mass m and curvature coupling in de Sitter space is investigated. It is shown that for an arbitrary, homogeneous, and isotropic, fourth-order adiabatic state for which the two-point function is infrared finite, T _ab approaches the Bunch–Davies de Sitter invariant value at late times if m ² + R > 0. In the case m = = 0, the energy–momentum tensor approaches the de Sitter invariant Allen–Folacci value for such a state. For m ² + R = 0 but m and not separately zero, it is shown that at late times T _ab grows linearly in terms of cosmic time leading to an instability of de Sitter space. The asymptotic behavior is again independent of the state of the field. For m ² + R < 0, it is shown that, for most values of m and , T _ab grows exponentially in terms of cosmic time at late times in a state dependent manner.     

Analytical and Experimental Study of Pressure Dynamics in a Pulsed Water Jet Device

Pulsed high-velocity water jets are of interest for breaking rocks and other materials. This paper describes a straightforward way of generating single water pulse with a hammer impacting a piston that rests on top of a chamber filled with water. This impacting action pressurises the water, expelling it at high velocity through a nozzle. A theoretical investigation is outlined aimed at gaining a better understanding of this system for generating water pulses. A computational model is developed to simulate the pressure dynamics in the chamber based on continuity and momentum equations for a compressible viscous flow. This model is used to optimise the relative sizes of the hammer and piston as well as the height of the water column to produce the highest velocity water pulse. The model was validated by building an experimental apparatus. In these experiments maximum pressures of about 200 MPa were measured inside the chamber over a time period of about 560???s. This produced a water pulse with maximum velocity of 600 m/s. Experiments were conducted with nozzle diameters between about 1 mm and 4 mm to study the effect of discharge volume on the pressure history. The results illustrate that although the peak attainable pressure decreases with an increase in nozzle diameter, the duration of the elevated pressure remains similar for all nozzles.     

Palladium nanoparticles supported on SiO2 by chemical vapor deposition (CVD) technique as efficient catalyst for Suzuki–Miyaura coupling of aryl bromides and iodides: selective coupling of halophenols

Nanoparticles of palladium were supported on SiO₂ by chemical vapor deposition technique. The obtained Pd nanocatalyst was characterized by various techniques. This catalyst was found to be very efficient for the selective cross‐coupling of hydroxyl‐substituted aryl iodides and bromide with arylboronic acids in water at room temperature to produce the corresponding hydroxyl‐substituted biaryls. Coupling of phenylboronic acid with aryl iodides and bromides carrying substituents other than hydroxy group was also performed efficiently in refluxing ethanol. Copyright © 2012 John Wiley & Sons, Ltd.     

Cyclodimerization by ring-closing metathesis: synthesis, computational, and biological evaluation of novel bis-azetidinyl-macrocycles

During our research on novel, non-traditional, bicyclic β-lactams as potential inhibitors of Penicillin Binding Proteins (PBPs), we focused on the synthesis of 1,3-bridged 2-azetidinones by RCM reaction from 1,3-bis-ω-alkenoyl-3(S)-amino-2-azetidinone precursors. Submitting the precursors to RCM, we faced an unexpected problem: cyclodimerization was the preferred outcome. This peculiar reactivity, explained by a computational study, led to unprecedented bis-azetidinyl-macrocycles acting as potent inhibitors of R39 D,D-carboxypeptidase, a bacterial model enzyme for PBPs.     

The Hydrothermal Synthesis of Petalite Mineral Phases and their Morphological Changing by Increasing of Temperature

In this investigation the Petalite minerals were synthesized hydrothermally at different temperatures from a glass with the composition Li₂CO₃:Al₂O₃: SiO₂ and the relation 1: 1: 8. On that occasion the following mineral phases arised:

• at low temperatures (410°C) α-petalite (unit cell å = 11.737 Å/b̊ = 5.17 Å/c̊ = 7.63 Å, space group P₂/a);
• At 490 °C α-petalite was splitted to quartz and an orthorhombic β₁-petalite (unit cell å = 18.24 Å/c̊ = 10.54 Å/c̊ = 10.57 Å, space group P_mC_n). β₁-petalite could be observated until 1000 °C.
• at 560 °C tetragonal β₂-petalite (unit cell å = 7.50 Å/c̊ = 9.07 Å, space group P 4₃2₁2) in parallel with β₁-petalite;
• Behind 750 °C β₂-petalite was not observed.
• Behind 900 °C a pseudohexagonal mineral phase developed from β₁-petalite. May be it is possible to indicate this phase as hexagonal (unit cell å = 5.217 Å/c̊ = 5.464 Å, space group P 6₂22 or P 6₄22). The author suggests to denote this phase as β₃-petalite.

     

The Hydrothermal Effect on Crystal Development and Electrical Conductivity of Li2CO3

Lithiumcarbonat was treated hydrothermally in the range of temperature from 80 °C to 600 °C. The Li₂CO₃-crystals of the starting material were monoclinic with the unit cell a = 8.39 Å, b = 5.00 Å, c = 6.21 Å, β = 114.5° and the space group C2/c (Zemann). During the increase of temperature the habit of the Li₂CO₃-crystals changed in the ranges of higher temperatures that they could be described as pseudocubic. In parallel with this development the electrical conductivity of the crystals also changed.