Evaluation of the origin of conformational and tautomeric preferences in N‐formylformamide – A quantum chemical study

Quantum chemical study of N‐formylformamide (NFF) was carried out at various theoretical levels and the determinate equilibrium conformations were recomputed at the high level ab initio methods such as G2MP2, G2, G3, and complete basis set (CBS)‐QB3. The computational results reveal that the amide resonance and intramolecular hydrogen bonding are two superior factors in determining the most stable conformation of diamide (DA) and amide–imidic (AI) acid tautomers, respectively. The evaluation of hydrogen bond energies predicts that the hydrogen bond (HB( strength of NFF is weaker than the malonaldehyde (MA). But the results of atoms in molecules (AIM(, natural bond orbital (NBO), and geometrical parameters are given a different order, E_HB(NFF) > E_HB(MA). Although the bond average energies of tautomerization process emphasized on more stability of AI tautomer, but our theoretical calculations reveal that the DA conformers are more stable than the AI ones. The population analyses of equilibrium conformations by NBO method also predict that the origin of tautomeric preference is mainly because of the electron delocalization of amide functional group, especially LP(N)→ π*_C?O charge transfer. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

A comparative study of open‐close and related rotamers methods to evaluate the intramolecular hydrogen bond energies in 3‐imino‐propen‐1‐ol and its derivatives

MP2 study of O? H…N intramolecular hydrogen bond (IMHB) in 3‐imino‐propen‐1‐ol and its derivatives were performed and their IMHB energies were obtained using the related rotamers and open‐close methods. Also the topological properties of electron density distribution and charge transfer energy associated with IMHB were gained by quantum theory of atoms in molecules and natural bond orbital theory, respectively. The computational results reveal that the related rotamers method energies are well correlates with geometrical parameters, topological parameters at hydrogen bond and ring critical points, integrated properties, proton transfer barrier and charge transfer energy of O? H…N unit. Surprisingly, it was found that the open‐close hydrogen bond energies cannot represent good linear correlations with these parameters. Consequently, we extrapolate a number of equations that can be used in estimation of O? H…N IMHB energy in complex biological systems. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Some results on stem covers of crossed modules

In this article, we prove the existence of stem covers for crossed modules, which generalizes the works of Schur (1904) [20] and Jones (1973) [11] in group theory. We also, using projective presentations, determine the structure of all stem covers of crossed modules whose second homologies are finite and, using this result, we give several results concerning them, which extend the classical ones for stem covers of groups.     

On strongly (<Emphasis Type="Italic">P</Emphasis>)-cyclic acts

By a regular act we mean an act such that all its cyclic subacts are projective. In this paper we introduce strong (P)-cyclic property of acts over monoids which is an extension of regularity and give a classification of monoids by this property of their right (Rees factor) acts.     

Microwave-assisted extraction combined with dispersive liquid-liquid microextraction as a new approach to determination of chlorophenols in soil and sediments

A new method was applied for extraction of five chlorophenols from soil and marine sediment samples. Microwave-assisted extraction coupled with dispersive liquid-liquid microextraction followed by semi-automated in-syringe back-extraction technique was used as an extraction technique. Microwave-assisted extraction was performed by using 2.0 mL of alkaline water at pH 10.0. After extraction, the pH of extraction solution was adjusted at 6.0 and dispersive liquid-liquid microextraction procedure was done using 1.0 mL of acetone as a disperser solvent and 37.0 μL of chlorobenzene as extraction solvent. About 20.0 ± 0.5 μL sedimented phase was collected after centrifugation step. Then, chlorophenols were back extracted into 20 μL of alkaline water at pH 12.0 within the microsyringe. Finally, 20.0 μL of aqueous solution was injected into high performance liquid chromatography with ultra violet detection for analysis. The obtained recovery and preconcentration factors for the analytes were in the range of 68.0-82.0% and 25-30, respectively, with relative standard deviations ≤7.6%. The limits of the detection were found in the range of 0.0005-0.002 mg/kg. The method provides a simple and fast procedure for the extraction and determination of chlorophenols in soil and marine sediment samples.     

Zonal modeling of radiative heat transfer in industrial furnaces using simplified model for exchange area calculation

The zonal analysis of industrial furnaces is considered with three-dimensional radiative heat transfer, incorporated with the mathematical zone method. In this method exchange areas are determined by simplified numerical integration in three dimensions for surface-surface, surface-gas and gas–gas zones for absorbing and emitting media. By focusing on new strategies to overcome the drawbacks of evaluating direct exchange areas, it is shown that the zone method is an effective numerical method for modeling three-dimensional thermal performance of gas-filled enclosures. Also the developed method for evaluating of exchange area is presented and compared with other methods in both sides of CPU time and accuracy. The method can decrease about 70% in error of calculation of some exchange areas as compared with the other numerical methods.     

Observational Constraints on the Modified Gravity Model (MOG) Proposed by Moffat: Using the Magellanic System

A simple model for the dynamics of the Magellanic Stream (MS), in the framework of modified gravity models is investigated. We assume that the galaxy is made up of baryonic matter out of context of dark matter scenario. The model we used here is named Modified Gravity (MOG) proposed by Moffat (J. Cosmol. Astropart. Phys. 003, 2005). In order to examine the compatibility of the overall properties of the MS under the MOG theory, the observational radial velocity profile of the MS is compared with the numerical results using the χ ² fit method. In order to obtain the best model parameters, a maximum likelihood analysis is performed. We also compare the results of this model with the Cold Dark Matter (CDM) halo model and the other alternative gravity model that proposed by Bekenstein (Phys. Rev. D 70:083509, 2004), so called TeVeS. We show that by selecting the appropriate values for the free parameters, the MOG theory seems to be plausible to explain the dynamics of the MS as well as the CDM and the TeVeS models.     

Thermal and mechanical properties of polysulfide/epoxy copolymer system: the effect of anhydride content

Polymerization of a ternary system containing polysulfide (PS), as a liquid elastomer, diglycidylether of bisphenol A resin, and phthalic anhydride was conducted using “design of experiment” technique. The polymerization progress with respect to concentration variations of components were studied by Fourier transform infrared spectroscopy. Fourier transform infrared spectroscopy studies showed that the anhydride plays a decisive role in curing reaction so that, in its absence, the epoxy/PS mixture becomes gel in about 2 hr, whereas, by addition of the anhydride, the pot life of the system can be extended to 48 hr. The cured samples were investigated by thermal gravimetry analysis and differential scanning calorimetry to evaluate thermal properties. Thermal gravimetry analysis and differential scanning calorimetry results indicated that two different soft and hard segments are formed, which have different thermal decompositions. The soft segment consists of loose etheric bonds, which are attributed to PS, and the hard segment is formed during the etherification and esterification reactions of the epoxy resin. Tensile strength test was performed to investigate the mechanical properties of PS/epoxy/anhydride‐cured systems. The results showed that the tensile strength, elongation‐at‐break, and the fracture energy of specimens are essentially dependent on PS/anhydride ratios. Two different segments impart high strength and ductility simultaneously. Copyright © 2013 John Wiley & Sons, Ltd.     

Application of crown ethers as stationary phase in the chromatographic methods

Recently, much attention has been paid to chromatographic characteristics and applications of crown ethers. These compounds were employed as chiral stationary phase for resolution of various racemic compounds in high performance chromatography and capillary electrochromatography techniques. Crown ethers also used in gas chromatography as the stationary phase. Recently, it has been found that, crown ethers also may be useful in cation chromatographic separation in ion chromatography for the determination of alkali and alkaline-earth cations, ammonium, and amines. In this paper we have an overview on these applications of crown ethers.     

Recent developments in microextraction techniques based on crown ethers

Sample preparation is essential for isolating desired components from complex matrices and greatly influences their reliable and accurate analysis. Microextraction techniques such as solid phase micro extraction and liquid–liquid–liquid micro extraction based on hollow fiber and also single drop micro extraction methods are new and effective sample preparation techniques. Crown ethers are heterocyclic chemical compounds that consist of a ring containing several ether groups. Recently crown ethers have been applied in these methods and increase efficiency and selectivity of these techniques. Here we review the application of crown ethers in various micro extraction techniques.