Simple synthesis of the novel Cu-MOF catalysts for the selective alcohol oxidation and the oxidative cross-coupling of amines and alcohols

A novel porous metal–organic framework {Cu₂(bbda)_0.5(Hbbda)_1.5(OAc)_1.5.8H₂O} (UoB-5) was synthesized under ultrasound irradiation by employing a new Schiff base ligand H₂bbda (4,4′(1,4-phenylene bis (azanylylidene)) bis (methanylylidene))dibenzoic acid) and was fully characterized. The microporous nature of UoB-5 was confirmed by gas-sorption measurements. This framework acted as a highly effective heterogeneous catalyst for the alcohol oxidation reaction with tert-butyl hydroperoxide (t-BuOOH) as an oxidant. The presence of coordinatively unsaturated metal sites in UoB-5 could be the reason for high performance in this reaction. Furthermore, using the long linker with the free -NC group and uncoordinated -N atom on the wall of the pores created UoB-5 an excellent candidate for the catalytic activities without activation of the framework. It was confirmed with the heterogeneous catalytic experiments on the one-pot tandem synthesis of imines from benzyl alcohols and anilines. Eventually, the new Cu-MOF (UoB-5) could be an alternative catalyst as a more economically favorable and environmentally friendly in the catalysis field.     

Synthesis, characterization, X-ray crystallography, acetyl cholinesterase inhibition and antioxidant activities of some novel ketone derivatives of gallic hydrazide-derived Schiff bases

Alzheimer's disease (AD) is the most common form of dementia among older people and the pathogenesis of this disease is associated with oxidative stress. Acetylcholinesterase inhibitors with antioxidant activities are considered potential treatments for AD. Some novel ketone derivatives of gallic hydrazide-derived Schiff bases were synthesized and examined for their antioxidant activities and in vitro and in silico acetyl cholinesterase inhibition. The compounds were characterized using spectroscopy and X-ray crystallography. The ferric reducing antioxidant power (FRAP) and 2,2-diphenyl-1-picrylhydrazyl (DPPH) assays revealed that all the compounds have strong antioxidant activities. N-(1-(5-bromo-2-hydroxyphenyl)-ethylidene)-3,4,5-trihydroxybenzohydrazide (2) was the most potent inhibitor of human acetyl cholinesterase, giving an inhibition rate of 77% at 100 μM. Molecular docking simulation of the ligand-enzyme complex suggested that the ligand may be positioned in the enzyme's active-site gorge, interacting with residues in the peripheral anionic subsite (PAS) and acyl binding pocket (ABP). The current work warrants further preclinical studies to assess the potential for these novel compounds for the treatment of AD.     

On the Structure of Sulfur/1,3-Diisopropenylbenzene Co-Polymer Cathodes for Li-S Batteries: Insights from Density-Functional Theory Calculations

Sulfur co-polymers have recently drawn considerable attention as alternative cathode materials for lithium-sulfur batteries, thanks to their flexible atomic structure and the ability to provide high reversible capacity. Here, we report on the atomic structure of sulfur/1,3-diisopropenylbenzene co-polymers (poly(S-co-DIB)) based on the insights obtained from density-functional theory calculations. The focus is set on studying the local structural properties, namely the favorable sulfur chain length (S_n with ) connecting two DIBs. In order to investigate the effects of the organic groups and sulfur chains separately, we perform series of atomic structure optimizations. We start from simple organic groups connected via sulfur chains and gradually change the structure of the organic groups until we reach a structure in which two DIB molecules are attached via sulfur chains. Additionally, to increase the structural sampling, we perform temperature-assisted minimum-energy structure search on slightly simpler model systems. We find that in DIB-S_n-DIB co-polymers, shorter sulfur chains with are preferred, where the stabilization is mostly brought about by the sulfur chains rather than the organic groups. The presented results, corresponding to the fully charged state of the cathode in the thermodynamic limit, have direct applications in the field of lithium-sulfur batteries with sulfur-polymer cathodes.     

Ellipsoidal anisotropy in linear elasticity: Approximation models and analytical solutions

The concept of ellipsoidal anisotropy, first introduced in linear elasticity by Saint Venant, has reappeared in recent years in diverse applications from the phenomenological to micromechanical modeling of materials. In this concept, indicator surfaces, which represent the variation of some elastic parameters in different directions of the material, are ellipsoidal. This concept recovers different models according to the elastic parameters that have ellipsoidal indicator surfaces. An interesting feature of some models introduced by Saint Venant is the formation of analytical solutions for basic problems of linear elasticity. This paper has two main objectives. First, an accurate definition of the variety of anisotropy called ellipsoidal is provided, which corresponds to a family of materials that depends on 12 independent parameters, including varieties of orthotropic and non-orthotropic materials. An explicit nondegenerate Green function solution is established for these materials. Then, it is shown that the ellipsoidal model recovers a variety of phenomenological and theoretical models used in recent years, specifically for geomaterials and damaged or micro-cracked materials. These models can be used to approximate the elastic parameters of any anisotropic material with different fitting qualities. A method to optimize the parameters will be given.     

Investigation of coupling length in a semi-cylindrical surface plasmonic coupler

We have investigated the performance of a nano-optical directional coupler based on gap plasmon waveguides. The coupler consists of two waveguides having a localized coupled plasmon propagating between two semi-cylindrical surfaces. After introducing a fundamental mode of studied waveguides, effects of the structure parameters on the coupling length are shown. Simulation results of the coupler obtained by the compact-2D finite-difference time-domain (FDTD) method comply with those derived by an analytic method with the aid of the finite-element frequency-domain (FEFD) software package of COMSOL.     

Investigation of the Electrochemical Behavior of Mesalazine on the Surface of a Glassy Carbon Electrode Modified with CNT/PPY Doped by 1,5‐Naphthalenedisulfonic Acid

A glassy carbon electrode (GCE) was modified with a thin layer of multiwalled carbon nanotubes (MWCNTs) and subsequently, electrochemically deposited poly‐pyrrole. The electrochemical behavior of mesalazine was studied on the surface of the modified electrode by applying linear sweep voltammetry (LSV). The electropolymerization process and the electrochemical response toward mesalazine were investigated in the presence of different aromatic anion dopants including, benzenesulfonic acid (BSA), 1,3‐benzenedisulfonic acid (1,3‐BDSA), 1,5‐naphthalenedisulfonic acid (1,5‐NDSA) and new coccine (NC). By using 1,5‐NDSA as dopant, a significant increase (～418 times) in the peak current of mesalazine was observed, in comparison to the bare GCE. Experimental variables such as drop size of the cast MWCNTs suspension, pH of the supporting electrolyte, accumulation conditions and the number of scans in the electropolymerization process were optimized by monitoring the LSV responses of mesalazine. Under the optimum conditions, two linear dynamic ranges of 0.01–0.1 µmol L^?1 and 0.1–1.0 µmol L^?1 with a detection limit of 3 nmol L^?1 were resulted for the voltammetric determination of mesalazine. The prepared electrode showed high sensitivity, stability and good reproducibility for determination of mesalazine. These properties made the prepared sensor suitable for the determination of mesalazine in pharmaceutical and clinical preparations.     

Broadcasting with hard deadlines in wireless multihop networks using network coding

Broadcasting with network coding mixes packets to minimize the number of transmissions, which improves the energy efficiency of wireless networks. On the other hand, delaying the transmissions increases coding opportunities at intermediate nodes, but increases the delay of packets. In this paper, we consider these two contradicting factors and study the problem of minimizing the number of transmissions in wireless networks while meeting the deadline constraints. We show that this problem is NP‐complete; therefore, we provide a heuristic to solve it. First, we construct broadcasting trees, each of them rooted at one source. We then specify overlapping conditions based on the constructed trees, to determine the number of transmissions each node has to perform without the deadline constraints. Then, we partition the set of packets such that coding is performed among the packets of the same partition, which does not result in deadline misses. Linear coding may not be applicable in some wireless networks because of its computational complexity. For these networks, we propose three XOR coding approaches, which rely only on local neighborhood information. Simulation results show that our techniques not only reduce the number of transmissions but also allow the majority of nodes to receive the packets on time. Copyright © 2013 John Wiley & Sons, Ltd.