Selected Reactions of Diethyl (E)‐1‐(bromomethyl)‐2‐cyanovinylphosphonate with Secondary and Tertiary Amines

An easy regio‐ and stereoselective synthesis of new nitrogenous molecules 2a–e was successfully realized via an effective coupling reaction of diethyl (E)‐1‐(bromomethyl)‐2‐cyanovinylphosphonate 1 with various secondary amines in methanol. Hence, the use of less and more bulky secondary amines gives rise, respectively, to the successive (S_N2′) substitution–isomerization and (S_N2) substitution derivatives 2a–c and 2d–e . Moreover, the addition of tertiary amines to 1 in the same reaction conditions, leads exclusively to the rearranged vinyl ether 3 in good yields.     

Weinstein–Sobolev Spaces of Exponential Type and Applications

In this paper, we introduce and study the Sobolev spaces of exponential type associated with the Weinstein operator, via some elements of harmonic analysis related to this operator. In particular, some properties, including completeness and imbedding theorem, are proved. Finally, using the theory of reproducing kernels, some applications are given for these spaces.     

Electroconvection between coaxial cylinders of arbitrary ratio subjected to strong unipolar injection

This study deals with the electroconvection phenomenon that takes place in a dielectric liquid layer placed between two annular electrodes and subjected to the action of an electric field.The full set of governing equations describing the combined Electro-Hydro-Dynamic (EHD) flow is directly solved with the finite volume method.The development of electroconvective motion is investigated in details in the case of strong injection when the emitter electrode is the inner cylinder.We first examine the stability of such flow. As in the plane–plane configuration we have highlighted the existence of a linear and non-linear critical electric Rayleigh numbers giving rise to a hysteresis loop. The flow structure under the effect of the electric field is analyzed and the distribution of electric charge density is presented. In particular we investigate the effect of various parameters involved in this configuration, such as the radius ratio, injection strength and electric Rayleigh number.A multicellular convective pattern is particularly observed and it is shown that the number of cells is increased when the annular gap is narrower. Finally a significant increase of the rotational speed of the vortex with the electric Rayleigh number is recorded.     

Raman study of cation effect on sulfate vibration modes in solid state and in aqueous solutions

Raman spectra of potassium, sodium, and ammonium sulfates (K₂SO₄, Na₂SO₄, and (NH₄)₂SO₄) are reported and analyzed. These sulfates have been investigated under two states: solid (anhydrous and hydrated) salts and aqueous solutions. The effects of monovalent ions (K⁺, Na⁺, and NH₄⁺) and hydration on the position of Raman lines assigned to internal vibrations of sulfate anion SO₄²⁻ are discussed. In solid salts, the line position of each Raman peak is shown to decrease with increasing radius of the cation. The main ν₁ mode of sulfate molecule is particularly affected. It is emphasized that this sensitivity in solid sulfates vanishes in aqueous solutions. As a consequence, this mode can be probed by Raman spectroscopy as the main signature of SO₄²⁻ to determine its concentration within a single calibration. Copyright © 2013 John Wiley & Sons, Ltd.     

Mixed thioalkyl-azoimine (SNN′)/α-diimine–ruthenium complexes: synthesis,characterization, DFT calculations,crystal structure and application as pre-catalysts for hydrogenation of acetophenone

Transition Metal Chemistry - Eight ruthenium complexes having thioalkyl-azoimine (SNN) ligands of two general types have been synthesized: (a) [Ru(L)(bipy)Cl](PF6) where {bipy = bipyridine,...     

Remarkable facets for selective monitoring of biomolecules by morphologically tailored CuO nanostructures

Journal of Solid State Electrochemistry - Remarkable selective analysis of biomolecules i.e., glucose and ascorbic acid on copper oxide facets was reported for the first time. The copper oxide...     

The Application of Fractal Transform and Entropy for Improving Fault Tolerance and Load Balancing in Grid Computing Environments

This paper applies the entropy-based fractal indexing scheme that enables the grid environment for fast indexing and querying. It addresses the issue of fault tolerance and load balancing-based fractal management to make computational grids more effective and reliable. A fractal dimension of a cloud of points gives an estimate of the intrinsic dimensionality of the data in that space. The main drawback of this technique is the long computing time. The main contribution of the suggested work is to investigate the effect of fractal transform by adding R-tree index structure-based entropy to existing grid computing models to obtain a balanced infrastructure with minimal fault. In this regard, the presented work is going to extend the commonly scheduling algorithms that are built based on the physical grid structure to a reduced logical network. The objective of this logical network is to reduce the searching in the grid paths according to arrival time rate and path’s bandwidth with respect to load balance and fault tolerance, respectively. Furthermore, an optimization searching technique is utilized to enhance the grid performance by investigating the optimum number of nodes extracted from the logical grid. The experimental results indicated that the proposed model has better execution time, throughput, makespan, latency, load balancing, and success rate.     

Chromatographic determination of sulfasalazine and its active metabolites: greenness assessment and application to spiked human plasma

Green TLC-densitometric and RP-HPLC methods were developed and validated for the determination of the active prodrug sulfasalazine (SZ), its active metabolite mesalazine (MZ) and the major active metabolite of mesalazine, N-acetyl-5-aminosalicylic acid (AS). In the developed TLC-densitometric method, chromatographic separation was carried out on TLC silica gel plates 60 F₂₅₄ using a developing system consisting of ethyl acetate–methanol–ammonia solution 33% (8:2.5:0.3, by volume) and then scanning the separated bands at 215 nm using hydrochlorothiazide as an internal standard with linearity ranges of 0.4–3, 0.4–2.4 and 0.3–2 for SZ, MZ and AS, respectively. The developed RP-HPLC method depended on chromatographic separation using a C₁₈ column with a solvent mixture of methanol–aqueous acetic acid solution (pH 5) as a mobile phase with gradient elution mode and UV scanning at 243 nm using pyrazinamide as internal standard with linearity ranges of 5–50, 5–40, and 3–20 for SZ, MZ and AS, respectively. US Food and Drug Administration guidelines were followed during validation of the methods. The greenness of the developed methods was estimated using the greenness profile and the Eco-Scale approach. Both methods passed the four quadrants of the greenness profile and had Eco-Scale score ˃75, thus they were considered to be green according to these approaches.     

Theoretical and experimental investigations of complexation with BF3.Et2O effects on electronic structures,energies and photophysical properties of Anil and tetraphenyl (hydroxyl) imidazol

The novel compounds (E)‐2‐(((4‐hydroxyphenyl)imino)methyl)phenol, Tetraphenyl (hydroxyl) imidazole and their corresponding Boron difluoride complexes were synthesized and characterized by spectroscopic techniques. Density functional theory calculations at B3LYP‐D3/6–311++G (d, p) level of theory were performed for the geometric parameters. The MEP surface studies were used to understand the behavior of molecules in terms of charge transfer and to determine how these molecules interact. We used the GIAO and the B3LYP‐D3 with a 6–311++ G (d, p) basis set to simulate the (¹H‐NMR and ¹⁹F‐NMR) and the IR spectra, respectively. The corresponding calculated results are in good agreement with the experimental data. The stability of the molecule arising from hyperconjugation interaction and charge delocalization were analyzed using NBO analysis. FMOs revealed the occurrence of charge transfer within the molecule. The complexation using BF₃.Et₂O was also found to have remarkable effects on the electrochemical properties of the studied molecules, where (b) and (d) present lower chemical stability, higher reactivity and higher polarizability than (a) and (c), respectively. Moreover, the energy gap of (a) and (c) decreased after complexation using BF₃.Et₂O, indicating the reliability of the electrochemical evaluation of LUMO and HOMO energy levels. These values are the factors explaining the possible charge transfer interaction within the molecule. The absorption and emission spectra of the model compound were also simulated and compared to experimental observations in the DMF solvent. The results of DFT calculations supported the structural and spectroscopic data and confirmed the structure modification of frontier molecular orbitals for BF₂ complexes as well as tunable potentials and energy levels.     

A new and facile tetrachlorosilane-promoted one-pot condensation for the synthesis of a novel series of tetracyclic 1,5-thiazepines

A new and facile approach for the one-pot synthesis of a novel series of tetracyclic 1,5-thiazepines is described. The reaction occurs through cyclocondensation of fused cyclic ketones, aromatic aldehydes, and 2-aminothiophenol using tetrachlorosilane as a promoter in methylene chloride at ambient temperature.