[PZnMo2W9O39]5− immobilized on ionic liquid-modified silica as a heterogeneous catalyst for epoxidation of olefins with hydrogen peroxide

The epoxidation of alkenes with hydrogen peroxide catalyzed by [PZnMo₂W₉O₃₉]^5-, ZnPOM, supported on ionic liquid-modified silica, Im-SiO₂, is reported. The immobilized catalyst, [ZnPOM@Im-SiO₂] was characterized by elemental analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR and UV–Vis spectroscopic methods. This new synthesized hybrid catalyst was applied for efficient epoxidation of various olefins with aqueous H₂O₂ in acetonitrile under reflux conditions. This solid catalyst can be easily recovered by simple filtration and reused several times without significant loss of its catalytic activity.     

A simple mathematical model for free vibration analysis of combined system consisting of framed tube,shear core,belt truss and outrigger system with geometrical discontinuities

Dynamic analysis of beam-like structure is significantly important in modeling real cases such as tall buildings, aircraft wings, spacecraft antennas and many other applications. This paper tries to determine the first natural frequency of tall buildings including framed tube, shear core, belt truss and outrigger system with multiple jumped discontinuities in the cross section of framed tube and shear core. In this regard, the entire length of the tall building is partitioned into uniform segments between each two successive discontinuity points. The effect of belt truss and outrigger system is modeled as a concentrated rotational spring applied at the belt truss and outrigger system location. Many cantilevered tall structures can be treated as cantilever bars with multiple jumped discontinuities in the cross section for the analysis of their free vibration. In this paper, the continuous approach was accepted and by using the Hamilton’s variational principle, the general form of governing equation for free vibration of tall building can be obtained. By applying the separation of variable method on time and space, the governing Partial Differential Equation (PDE) of motion is reduced to an Ordinary Differential Equation (ODE) with one variable coefficient while the other coefficients are constant based on the assumption that the transverse displacement is a harmonic vibration. To find exact solution of ODE, we must have exact distribution of EI(x), AG(x), N(x) and m(x) in the height of the structure. Some of these parameters such as EI(x), AG(x) and m(x), are constant throughout the height of each segment. These parameters can be expressed exactly by using of multi criteria function, while N(x) is variable in the height of each segment. Therefore, the ODE by using the method of variable separation and partitioned method can be expressed for each segment. We must apply the continuity conditions in conjunction with different segments for obtaining unique mode shape for mentioned system. Tall building characteristics matrix can be derived based on the boundary conditions and the continuity conditions applied at the partitioned points. This matrix is particularly used to find combined system first natural frequency and mode shape. Three numerical examples with different stepped discontinuities in their cross sections are studied to demonstrate the reliability of this method. The results of the proposed mathematical model give a good understanding of the structure’s dynamic characteristics; it is easy to use, yet reasonably accurate and suitable for quick evaluations during the preliminary design stages which require less time.     

RAFT-mediated emulsion polymerization of vinyl acetate: a challenge towards producing high molecular weight poly(vinyl acetate)

The preparation of poly(vinyl acetate) with well-controlled structure has received a great deal of interest in recent years because of a large number of developments in living radical polymerization techniques. Among these techniques, the use of reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization has been employed for the controlled polymerization of vinyl acetate due to the high susceptibility of this monomer towards chain transfer reactions. Here, a novel water-soluble N,N-dialkyl dithiocarbamate RAFT agent has been prepared and employed in the emulsion polymerization of vinyl acetate. The kinetic results reveal that the polymerization nucleation mechanism changes from homogeneous to micellar and RAFT-generated radicals can change the kinetic behavior from conventional emulsion polymerization to living radical polymerization. At higher concentrations of the modified RAFT agent, as a result of an aqueous phase reaction between RAFT and sulfate radicals, relatively more hydrophobic radicals are generated, which favors entry and propagation into micelles swollen with monomer. This observation was determined from the investigation of the polymerization rate and measurements of the average particle diameter and the number of particles per liter of the aqueous phase. Molecular weight analysis also demonstrated the participation of the RAFT agent in the polymerization in such a way as to restrict chain transfer reactions. This was determined by examining the evolution of polymer chain length and attaining higher molecular weights, even up to 50?% greater than the samples obtained from the conventional emulsion polymerization of vinyl acetate in the absence of the synthesized modified RAFT agent.     

Water assisted growth of C₆₀ rods and tubes by liquid-liquid interfacial precipitation method

C?? nanorods with hexagonal cross sections are grown using a static liquid-liquid interfacial precipitation method in a system of C??/m-dichlorobenzene solution and ethanol. Adding water to the ethanol phase leads instead to C?? tubes where both length and diameter of the C?? tubes can be controlled by the water content in the ethanol. Based on our observations we find that the diameter of the rods/tubes strongly depends on the nucleation step. We propose a liquid-liquid interface growth model of C?? rods and tubes based on the diffusion rate of the good C?? containing solvent into the poor solvent as well as on the size of the crystal seeds formed at the interface between the two solvents. The grown rods and tubes exhibit a hexagonal solvate crystal structure with m-dichlorobenzene solvent molecules incorporated into the crystal structure, independent of the water content. An annealing step at 200 °C at a pressure < 1 kPa transforms the grown structures into a solvent-free face centered cubic structure. Both the hexagonal and the face centered cubic structures are very stable and neither morphology nor structure shows any signs of degradation after three months of storage.     

Spectroscopic studies on Solvatochromism of mixed-chelate copper(II) complexes using MLR technique

Mixed-chelate copper(II) complexes with a general formula [Cu(acac)(diamine)]X where acac=acetylacetonate ion, diamine=N,N-dimethyl,N'-benzyl-1,2-diaminoethane and X=BPh(4)(-), PF(6)(-), ClO(4)(-) and BF(4)(-) have been prepared. The complexes were characterized on the basis of elemental analysis, molar conductance, UV-vis and IR spectroscopies. The complexes are solvatochromic and their solvatochromism were investigated by visible spectroscopy. All complexes demonstrated the positive solvatochromism and among the complexes [Cu(acac)(diamine)]BPh(4)·H(2)O showed the highest Δν(max) value. To explore the mechanism of interaction between solvent molecules and the complexes, different solvent parameters such as DN, AN, α and β using multiple linear regression (MLR) method were employed. The statistical results suggested that the DN parameter of the solvent plays a dominate contribution to the shift of the d-d absorption band of the complexes.     

Selective conversion of C=N bonds to their corresponding carbonyl compounds by the tribromoisocyanuric acid/wet SiO2 system as a novel reagent

Abstract  

Tribromoisocyanuric acid/wet SiO₂ was used for the conversion of C=N bonds to their corresponding carbonyl compounds in oximes, semicarbazones, azines, and Schiff bases. The interesting feature of this system is that in those oximes, semicarbazones, azines, and Schiff bases which have conjugated or unconjugated C=C bonds, the C=N bond will selectively change to the relevant C=O bond while the conjugated or unconjugated C=C bond will remain intact.     

A phosphoryl to spiro-bicyclophosphorane transformation via β-amidic proton elimination in phosphorylated hydrazides

The reaction between phosphoryl-containing reagents and hydrazides has been studied. The tetrahedral phosphoryl structure is transformed into a spiro-bicyclophosphorane system with trigonal bipyramidal geometry by the elimination of a β-amidic proton in the reaction between a hydrazide and phosphoryl reagents with at least two leaving groups (Cl) bound to the phosphorus atom, such as POCl₃ or PhPOCl₂. In the spiro-bicyclophosphorane structure, the CN imine bond is formed upon β-amidic proton elimination, leading to the conversion of the CO into a C-O bond and the formation of a P-O bond. All of these structural rearrangements are supported by X-ray crystallography data, and NMR and IR experiments.     

An efficient regioselective synthesis of highly functionalized 3-oxo-2,3-dihydro-5H-thiazolo[3,2-a]pyrimidines via an isocyanide-based three-component reaction

We present a novel, convenient, and efficient method for synthesizing polysubstituted 3-oxo-2,3-dihydro-5H-[1,3]thiazolo[3,2-a]pyrimidines via a three-component reaction. The zwitterions generated from the reaction of isocyanides and dialkyl acetylenedicarboxylates react with 2-imino-1,3-thiazolidin-4-one to produce the title compounds in good yields.