Chemical and electrochemical procedures for the synthesis of diisopropyltetrahydroquinoxalinedione derivatives

Diisopropyltetrahydroquinoxalinedione derivatives are synthesized from the reaction of various catechols with N,N′-diisopropylethylenediamine. Both chemical and electrochemical methods give the same products. While the chemical synthesis is faster, the electrochemical synthesis provides higher yields.     

Stereoselective synthesis of helical dihydrodipyrrolophenanthroline and hindrance hexa tert‐butyl carboxylatodipyrrolophenanthroline from reaction between 1,10‐phenanthroline and dialkyl acetylenedicarboxylates

High hindrance Hexa tert‐butoxy carbonyl dipyrrolophenanthroline and helical dihydropyrrolophen‐anthroline compounds were prepared from reactions between di tert‐butyl acetylenedicarboxylate and 1,10‐phenanthroline in polar solvents media.     

Reduction in the Resonance Error in Numerical Homogenization II: Correctors and Extrapolation

This paper is the follow-up of Gloria (Math Models Methods Appl Sci 21(8):1601–1630, 2011). One common drawback among numerical homogenization methods is the presence of the so-called resonance error, which roughly speaking is a function of the ratio \(\frac{\varepsilon }{\rho }\), where \(\rho \) is a typical macroscopic lengthscale and \(\varepsilon \) is the typical size of the heterogeneities. In the present work, we make a systematic use of regularization and extrapolation to reduce this resonance error at the level of the approximation of homogenized coefficients and correctors for general non-necessarily symmetric stationary ergodic coefficients. We quantify this reduction for the class of periodic coefficients, for the Kozlov subclass of almost-periodic coefficients, and for the subclass of random coefficients that satisfy a spectral gap estimate (e.g., Poisson random inclusions). We also report on a systematic numerical study in dimension 2, which demonstrates the efficiency of the method and the sharpness of the analysis. Last, we combine this approach to numerical homogenization methods, prove the asymptotic consistency in the case of locally stationary ergodic coefficients, and give quantitative estimates in the case of periodic coefficients.     

Computational design and multivariate optimization of an electrochemical metoprolol sensor based on molecular imprinting in combination with carbon nanotubes

This work describes the development of an electrochemical sensor based on a new molecularly imprinted polymer for detection of metoprolol (MTP) at ultra-trace level. The polypyrrole (PPy) was electrochemically synthesized on the tip of a pencil graphite electrode (PGE) which modified whit functionalized multi-walled carbon nanotubes (MWCNTs). The fabrication process of the sensor was characterized by cyclic voltammetry (CV) and the measurement process was carried out by differential pulse voltammetry (DPV). A computational approach was used to screening functional monomers and polymerization solvent for rational design of molecularly imprinted polymer (MIP). Based on computational results, pyrrole and water were selected as functional monomer and polymerization solvent, respectively. Several significant parameters controlling the performance of the MIP sensor were examined and optimized using multivariate optimization methods such as Plackett–Burman design (PBD) and central composite design (CCD). Under the selected optimal conditions, MIP sensor was showed a linear range from 0.06 to 490 μmol L⁻¹ MTP, a limit of detection of 2.88 nmol L⁻¹, a highly reproducible response (RSD 3.9%) and a good selectivity in the presence of structurally related molecules. Furthermore, the applicability of the method was successfully tested with determination of MTP in real samples (tablet, and serum).     

Synthesis and crystal structure of the dinuclear copper(II) Schiff base complex μ‐hydroxido‐μ‐chlorido‐bis{[bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine]chloridocopper(II)} dichloromethane sesquisolvate

Transition metal complexes of Schiff base ligands have been shown to have particular application in catalysis and magnetism. The chemistry of copper complexes is of interest owing to their importance in biological and industrial processes. The reaction of copper(I) chloride with the bidentate Schiff base N,N′‐bis(trans‐2‐nitrocinnamaldehyde)ethylenediamine {Nca₂en, systematic name: (1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]} in a 1:1 molar ratio in dichloromethane without exclusion of air or moisture resulted in the formation of the title complex μ‐chlorido‐μ‐hydroxido‐bis(chlorido{(1E,1′E,2E,2′E)‐N,N′‐(ethane‐1,2‐diyl)bis[3‐(2‐nitrophenyl)prop‐2‐en‐1‐imine]‐κ²N,N′}copper(II)) dichloromethane sesquisolvate, [Cu₂Cl₃(OH)(C₂₀H₁₈N₄O₄)₂]·1.5CH₂Cl₂. The dinuclear complex has a folded four‐membered ring in an unsymmetrical Cu₂OCl₃ core in which the approximate trigonal bipyramidal coordination displays different angular distortions in the equatorial planes of the two Cu^II atoms; the chloride bridge is asymmetric, but the hydroxide bridge is symmetric. The chelate rings of the two Nca₂en ligands have different conformations, leading to a more marked bowing of one of the ligands compared with the other. This is the first reported dinuclear complex, and the first five‐coordinate complex, of the Nca₂en Schiff base ligand. Molecules of the dimer are associated in pairs by ring‐stacking interactions supported by C—H…Cl interactions with solvent molecules; a further ring‐stacking interaction exists between the two Schiff base ligands of each molecule.     

Langmuir-Blodgett films of cellulose nanocrystals: preparation and characterization

The goal of this work is the preparation of monolayers of cellulose I nanocrystals providing flat crystalline cellulose surfaces. Suspensions of cellulose nanocrystals were prepared by hydrolyzing ramie and tunicin fibers with sulfuric acid. Due to surface grafted sulfate groups, the negatively charged, rod-like cellulose nanocrystals were found to form stable layers at the air-water interface in the presence of a cationic amphiphilic molecule such as dioctadecyldimethylammonium (DODA) used in this work. These layers were formed at different cellulose-DODA weight ratios, compressed and analyzed by tensiometry, ellipsometry and Brewster angle microscopy. At low cellulose concentrations the layers are discontinuous, becoming dense and homogeneous upon reaching a critical weight ratio, which depends on the aspect ratio of the cellulose nanocrystals. After transfer onto silicon wafers, the surface composition and morphology as well as the thickness of the films were examined by X-ray photoelectron spectroscopy, ellipsometry and atomic force microscopy. The results indicate that they are monolayer films, well structured, relatively smooth and pure. These films offer a crystalline and easily reproducible model cellulose surface.     

Dependence of nonlinear elasticity on filler size in composite polymer systems

Nanosized filler particles enhance the mechanical properties of polymer composites in a size-dependent fashion. This is puzzling, because classical elasticity is inherently scale-free, and models for the elasticity of composite systems never predict a filler-size dependence. Here, we study the industrially important system of silica-filled rubbers, together with a well-characterized model-filled crosslinked gel and show that at high filler content both the linear and nonlinear elastic properties of these systems exhibit a unique scaling proportional to the cube of the volume fraction divided by the particle size. This remarkable behavior makes it possible to predict the full mechanical response of particle-filled rubbers for small but finite deformations based solely on the rheology of the matrix and the size and modulus of the filler particles.     

Hydrophobically modified poly (acrylic acid) using calix[4]arene derivative. Ionophoric properties and extraction abilities toward alkali metal cations

p‐t‐Butyl calix[4]arene diol (distal cone) (1) was grafted with poly (acrylic acid) (PAA) to obtain hydrophobically modified PAA (PAA‐C) bearing calixarene moieties. The grafting method includes the direct esterification reaction of PAA with calixarene diol 1 which was carried out in a system of tosyl chloride (TsCl), pyridine (Py), and N,N‐dimethylformamide (DMF). The grafting yield was studied using different molar ratios of PAA to calix[4]arene diol 1, temperature, and reaction time. The chemical composition of the PAA‐C was studied by IR and ¹H NMR spectroscopy. Also, the morphology of PAA‐C was evaluated by scanning electron microscopy. The PAA‐C had different solubility and thermal properties. The extraction ability measurements of modified PAA toward alkali metal cations (Na⁺, K⁺, Cs⁺) and Ag⁺ showed a remarkable efficiency and selectivity of PAA‐C toward Na⁺. The main goal of this work was to design hydrophobically modified PAA with binding ability that is suitable for ion selective membranes and chemical sensor devices such as ion‐specific electrodes, semipermeable membranes, and quartz microbalances. Copyright © 2009 John Wiley & Sons, Ltd.     

Photodegradation kinetics of some thiols and thiones in aqueous suspension of zinc oxide

Photodegradation of several thiols and thiones including 2-pyrimidinethiol, thiazolidine-2-thione, imidazolidine-2-thione, 1,2,4- triazole 3-thiol and 2,5-dimercapto- 1,3,4-thiadiazole have been studied in aerated aqueous solution using zinc oxide under irradiation with 400W high pressure mercury lamp. Rate constants span the range from 2.44 x 10(-2) min x (-1) to 1.76 x 10(-1) min x (-1). The slower degradation rate of 2-imidazoline 2-thione could be related to oxidation potential of the corresponding ring. The Langmuir-Hinshelwood (L-H) rate constant k(r) and adsorption constant, (KA) for all five thiols and thiones are reported.     

Approximate solution of non-Newtonian viscoelastic fluid flow on a turbine disc for cooling purposes by using Adomian decomposition method

In this work, a powerful semi-analytical method, called Adomian decomposition method (ADM) is introduced to obtain the exact solution of heat transfer equation of a non-Newtonian fluid flow in an axisymmetric channel with a porous wall which is useful for turbine cooling applications. This method is employed to obtain the expressions for velocity and temperature fields. Then, the influence of the two dimensionless numbers: the Prandtl number (Pr) and the Reynolds number (Re) for the dynamic forces have been considered. Comparisons are made between the numerical method (NM) solution, Homotopy perturbation method (HPM), Variation iteration method (VIM) and the results of Adomian decomposition method (ADM). The results reveal that this method is very effective and simple and can be applied for other nonlinear problems.