Synthesis and Characterization of Copper(II)–Cysteine/SiO2–Al2O3 as an Efficient and Reusable Heterogeneous Catalyst for the Oxidation of Aromatic Alcohols

In the present study, heterogeneous copper(II)–cysteine/SiO₂–Al₂O₃ catalyst was successfully prepared by a simple adsorption method. The physical and chemical properties of Cu(II)–cysteine/SiO₂–Al₂O₃ were investigated by X-ray diffraction, thermal gravimetric analyzer, FT–IR spectroscopy, Brunauer–Emmett–Teller, UV–Vis spectroscopy, scanning electron microscopy and atomic absorption spectrometer. The obtained composite was effectively employed as catalyst for selective oxidation of various aromatic alcohols to corresponding aldehydes in high yields using hydrogen peroxide as an oxidant under mild condition. The catalyst can be recycled over five times without significant loss of activity.     

Analysis of MTHFR and MTRR Gene Polymorphisms in Iranian Ventricular Septal Defect Subjects

Ventricular septal defect (VSD) is one of the most common types of congenital heart defects (CHD). There are vivid multifactorial causes for VSD in which both genetic and environmental risk factors are consequential in the development of CHD. Methionine synthase reductase (MTRR) and methylenetetrahydrofolate reductase (MTHFR) are two of the key regulatory enzymes involved in the metabolic pathway of homocysteine. Genes involved in homocysteine/folate metabolism may play an important role in CHDs. In this study; we determined the association of A66G and C524T polymorphisms of the MTRR gene and C677T polymorphism of the MTHFR gene in Iranian VSD subjects. A total of 123 children with VSDs and 125 healthy children were included in this study. Genomic DNA was extracted from the buccal cells of all the subjects. The restriction fragment length polymorphism polymerase chain reaction (PCR-RFLP) method was carried out to amplify the A66G and C524T polymorphism of MTRR and C677T polymorphism of MTHFR genes digested with Hinf1, Xho1 and Nde1 enzymes, respectively. The genotype frequencies of CC, CT and TT of MTRR gene among the studied cases were 43.1%, 40.7% and 16.3%, respectively, compared to 52.8%, 43.2% and 4.0%, respectively among the controls. For the MTRR A66G gene polymorphism, the genotypes frequencies of AA, AG and GG among the cases were 33.3%, 43.9% and 22.8%, respectively, while the frequencies were 49.6%, 42.4% and 8.0%, respectively, among control subjects. The frequencies for CC and CT genotypes of the MTHFR gene were 51.2% and 48.8%, respectively, in VSD patients compared to 56.8% and 43.2% respectively, in control subjects. Apart from MTHFR C677T polymorphism, significant differences were noticed (p < 0.05) in C524T and A66G polymorphisms of the MTRR gene between cases and control subjects.     

Study of payment scheduling problem to achieve client–contractor agreement

This paper aims to determine simultaneously the amount, timing, and location of progress payments in projects in order to achieve a set of equitable solutions in the client–contractor negotiation process. The objective function tries to minimize the distance between the final solutions and the best achievable solutions of the client and the contractor. Due to combinatorial nature of the proposed problem, an iterative two-stage search method is proposed. In the first stage, a set of payments is determined to maximize the contractor's net present value (NPV), another set to maximize the client's NPV, and another one to minimize the objective function. In the second stage, activities are rescheduled to improve the solutions by fixing the amount and location of progress payments. A hybrid meta-heuristic algorithm named GASA, along with a simulated annealing (SA) and a genetic algorithm (GA), is introduced for the first stage, while the activities are optimally scheduled in the second stage. It has been shown that SA is better for the contractor’s objective function and GA for the client’s objective function, but GASA is the best in all situations; besides, the proposed method has represented to be an efficient approach to obtain non-dominated solutions in the client–contractor negotiation process.     

On multiple‐delay output feedback stabilization of LTI plants

We develop a control methodology for linear time‐invariant plants that uses multiple delayed observations in feedback. Using the special coordinate basis, we show that multiple‐delay controllers can always be designed to stabilize minimum‐phase plants, and identify a class of non‐minimum‐phase plants that can be stabilized using these controllers. Copyright © 2009 John Wiley & Sons, Ltd.     

Glassy carbon electrode modified with a bilayer of multi-walled carbon nanotube and polypyrrole doped with new coccine: Application to the sensitive electrochemical determination of Sumatriptan

A promising electrochemical sensor was developed based on a layer by layer process by electro-polymerization of pyrrole in the presence of new coccine (NC) as dopant anion on the surface of the multi-walled carbon nanotubes (MWCNTs) pre-coated glassy carbon electrode (GCE). The modified electrode was used as a new and sensitive electrochemical sensor for voltammetric determination of sumatriptan (SUM). The electrochemical behavior of SUM was investigated on the surface of the modified electrode using linear sweep voltammetry (LSV). The results showed a remarkable increase (∼12 times) in the anodic peak current of SUM in comparison to the bare GCE. The effect of experimental variables such as, drop size of the casted MWCNTs suspension, pH of the supporting electrolyte, accumulation conditions and the number of cycles in the electro-polymerization process on the electrode response was investigated. Under the optimum conditions, the modified electrode showed a wide linear dynamic range of 0.02–10.0 μmol L⁻¹ with a detection limit of 6 nmol L⁻¹ for the voltammetric determination of SUM. The prepared electrode showed high sensitivity, stability and good reproducibility in response to SUM. This sensor was successfully applied for the accurate determination of trace amounts of SUM in pharmaceutical and clinical preparations.     

Performance evaluation of modified rotating-jet electrospinning method by investigating the effect of collector size on the nanofibers alignment

Modified rotating-jet electrospinning method (MRJM) is a new electrospinning technique with a novel setup including two metallic concentric hollow cylinders for generating highly aligned fibers. In this report, an experimental study was carried out to evaluate the effectiveness of MRJM for generating highly aligned nanofibers. For this purpose, the effect of voltage in the range of 10–22 kV, inner collector diameter in the range of 20–50 cm, and outer collector diameter in the range of 30–60 cm, on alignment degrees of electrospun fibers were explored and the results for each set of parameters were compared with those obtained for rotating-jet electrospinning method (RJM). The obtained results indicated that the alignment degrees of electrospun fibers in MRJM were significantly higher than those of RJM. The maximum achievable alignment degree in MRJM was around 82 % that was higher than the corresponding maximum value (40 %) of RJM. Although the effect of applied voltage on the degree of alignment in MRJM was observed to be negligible, it was experimentally proved that by manipulating the outer cylinder diameter, the degree of alignment can be increased up to 20 %. To achieve a conceptual understanding of the reason for significant influence of the outer cylinder on the elecrospinning performance, a formula was derived according to the Gauss’s law in the last part of this paper that relates the electric field strength inside the region between the inner cylinder and the spinneret to the radii of inner and outer cylinders.     

Quantum chemical studies on molecular conformations,energetic and intramolecular hydrogen bonding in ground and electronic excited state of (thioxosilyl) ethyleneselenol

In this work, a conformational analysis of (thioxosilyl) ethyleneselenol was performed using several computational methods, including density-functional theory (DFT) (B3LYP), MP2 and G2MP2. Harmonic vibrational frequencies were estimated at the same levels to confirm the nature of the stationary points found and also to account for the zero point vibrational energy correction. MES-1 and TES-1 conformers exhibit hydrogen bonding. This feature, although is not the dominant factor in the stability of conformers, appears to be of foremost importance to define the geometry of the molecule. Two intramolecular hydrogen bonds established between the polar groups were identified by the structural geometric parameters. These involved the thiol and selenol functional groups and were identified and characterized by the frequency shift in their stretching vibration modes. Furthermore, the excited-state properties of intramolecular hydrogen bonding have been investigated theoretically using the time-dependent DFT method. The influence of the solvent on the stability order of conformers and the strength of intramolecular hydrogen bonding was considered using the PCM (polarizable continuum model), SCI-PCM (self consistent isodensity-polarizable continuum model) and IEF-PCM (integral equation formalism-polarizable continuum model) methods. The “atoms in molecules” theory of Bader was used to analyze critical points and to study the nature of hydrogen bond in these systems. Natural bond orbital (NBO) analysis was also performed for better understanding the nature of intramolecular interactions. The calculated highest occupiedmolecular orbital and lowest unoccupied molecular orbital energies show that charge transfer occur within the molecule. Further verification of the obtained transition state structures was implemented via intrinsic reaction coordinate analysis. Calculations of the ¹H NMR chemical shift at the GIAO/B3LYP/6–311++G** level of theory are also presented.     

Comparison of bolted end plate and T-stub connections sensitivity to bolt diameter on cyclic behavior

Considering the construction limitations, proper and correct design of connections is vital and of great importance. At the construction stage, it is probable to use a connection bolt with a diameter less than the design assumptions. It can occur due to an imperfection in construction or even to changes in the function of the building. The unforeseen changes can increase the structural load, and consequently the moment and shear force demand values. Therefore, the present paper is aimed to examine the sensitivity of the bolted connections to the diameter of bolts using a numerical method. The results show that bolted T-stub connections are more sensitive to bolt diameter than end plate connections. Hence, the bolted end plate connections are recommended where the imperfection in construction or changes in function of the building is probable. Moreover, in construction of bolted connections, if changing the number of bolts regarding the constant total cross sectional area is considered, it is recommended to use the symmetric arrangement of bolts on each beam flange. In design of connections for a particular frame according to AISC, the moment capacity of T-stub connection is higher than that of end plate connection. However, the total energy absorptions of these connection types are approximately equal.     

In-situ EQCM evaluation of the formation of UPD and OPD during electrodeposition of Pb on gold

Underpotential (UPD) and overpotential (OPD) deposition of Pb from a perchlorate solution on gold substrate was studied using in-situ electrochemical quartz crystal microbalance (EQCM) method. Cyclic voltammograms and current-transients recorded during potentiostatic electrochemical deposition were measured simultaneously with EQCM data including frequency and resistance. Results show that underpotential deposition (UPD) of Pb occurs before overpotential deposition (OPD) of Pb starts to grow, based on both massogram and cyclic voltammogram. The OPD of Pb grows at higher overpotentials which significantly influence the mechanism of nucleation and growth. EQCM reveals that the mass to charge ratio of OPD is different at different overpotentials, owing to the mechanism of nucleation and growth and possible roughening of grown Pb or hydrogen evolution. A comparison between our experimental data with the Scharifker-Hills theory based on non-dimensional plots shows an instantaneous mechanism. Scanning electron microscope taken from the electrodeposited lead on gold confirms the behaviour exhibiting almost same size of nuclei.