Connecting free volume with shape memory properties in noncytotoxic gamma‐irradiated polycyclooctene

The free volume holes of a shape memory polymer have been analyzed considering that the empty space between molecules is necessary for the molecular motion, and the shape memory response is based on polymer segments acting as molecular switches through variable flexibility with temperature or other stimuli. Therefore, thermomechanical analysis (TMA) and positron annihilation lifetime spectroscopy (PALS) have been applied to analyze shape recovery and free volume hole sizes in gamma‐irradiated polycyclooctene (PCO) samples, as a noncytotoxic alternative to more conventional PCO crosslinked via peroxide for future applications in medicine. Thus, a first approach relating structure, free volume holes and shape memory properties in gamma‐irradiated PCO is presented. The results suggest that free volume holes caused by gamma irradiation in PCO samples facilitate the recovery process by improving movement of polymer chains and open possibilities for the design and control of the macroscopic response. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1080–1088     

Experimental validation of distinct element simulation for dynamic wheel–soil interaction

The deformation behaviour of the soil during dynamic wheel–soil interaction was studied by using the discontinuum modelling technique, distinct or discrete element method (DEM). The simulation model was developed using DEM for two types of soil, soil-A (coarse sand) and soil-B (medium sand). A transparent sided soil bin was used to observe the soil deformation. Three CCD video camera photographic images of the validation experiments were analyzed and compared with the simulation program results.This paper presents the simulation and validation results for two types of soil at three different vertical loadings of 4.9, 9.8 and 14.7 N. Wheel sinkage, vertical and horizontal draft force acting on the rigid wheel and the soil deformation images from the validation experiments were some of the data used to compare the simulation program results with the validation experiments. The simulation program was helpful to understand the complex deformation behaviour of the soils. The simulated results for the deformation behaviour of soil-B showed better correlation with the validation experiments than soil-A. The results obtained have also been compared with the previous work on DEM to explain phenomena such as the high simulated sinkage of the rigid wheel.     

Evaluation of Polyphenols in Wine by Voltammetric Techniques with Screen Printed Carbon Electrodes

The electrochemical oxidation processes that occur during a voltammetric assay in wine samples lead to the formation of species that obstructs the surface and reduce their active area. This effect is critical for screen printed carbon electrodes (SPCE) and leads to abnormal low values of the total polyphenols content of wines, ca. 72 % lower than those obtained with glassy carbon electrodes. This effect was examined using 10 red and Port wine samples. Mechanical polishing and electrochemical‐based treatments for the removal of this fouling layer were tested. The best results were obtained by electrochemical activation in at a constant potential of 1.2 V during 100 s Na₂CO₃ saturated solution, and by polishing. The success of some of these treatments brings an added value to SPCE, as it opens the possibility of their reuse in the wine analysis. This outcome is particularly relevant for quality control where a huge number of analysis is performed and the reduction of cost may dictates the choice of the analytical method.     

6,6′-Thiobis(methylene)-β-cyclodextrin dimer as a dimeric host and reusable promoter for synthesis of chromenones in water

Herein, two unit of β-cyclodextrin linked by thiomethylene bridge was synthesized and employed as a novel efficient supramolecular host for the synthesis of biologically active chromenones templates via three-component single-pot reaction. A possible reaction mechanism through molecular complexation is suggested based on 2D ROESY NMR spectroscopic analysis. Moreover, the catalyst could be easily recycled, while a 94% yield and 89% rate of catalyst recovery could be achieved after four cycles of catalyst recycling. Environmentally benign reaction conditions, excellent yields, and avoidance of organic solvent and conventional isolation as well as purification are the noteworthy credits of this developed protocol.     

Tandem and chemoselective synthesis of benzil derivatives from styrene and arene diazonium salts

A facile and practically applied protocol for synthesis of benzil derivatives using styrene and arene diazonium salts is reported. Pd(OAc)₂/SeO₂ catalytic system was found to be efficient for chemoselective synthesis of benzil. Selenium dioxide works well as an oxidant under milder reaction conditions. Moderate to very good yields of the desired products were obtained.     

Nickel‐Catalyzed Cross‐Coupling of Alkyl Zinc Halides for the Formation of C(sp2)?C(sp3) Bonds: Scope and Mechanism

Optimal conditions for a general Ni‐catalysed Negishi cross‐coupling of alkyl zinc halides with aryl, heteroaryl and alkenyl halides have been determined. These conditions allow the reaction to take place smoothly, with low catalyst loading, and in the presence of a wide variety of functional groups to afford products in good yields at room temperature. DFT studies on the mechanism support the occurrence of a catalytic cycle involving transmetalation of the alkyl zinc halide to Ni^I followed by oxidative addition of the haloarene and C? C reductive elimination.     

Thermoset Alkyd-Acrylic Hybrid Emulsions for Coatings

Alkyd acrylic hybrid emulsions can offer cost/performance advantages over common 1K coatings such as polyurethane dispersions (PUDs), acrylic emulsions and blends. Hybrid emulsions with different ratios of alkyd resin to acrylic monomers were synthesized. Emulsion with resin-to monomer ratio of 1:1 (wt/wt) with total solids as high as 50% had a shelf stability of more than 8 months. Morphology of hybrid emulsions was studied by scanning electron microscopy. Hybrid emulsions were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Films obtained from the hybrid emulsions were found to be homogeneous and exhibited excellent thermal and coating properties.     

Phytosynthesis of Silver Nanoparticles Using Walnut (Juglans regia) Bark with Characterization of the Antibacterial Activity against Streptococcus mutans

A green method using Juglans regia bark extract was used to synthesize silver nanoparticles at room temperature with monitoring by absorption spectroscopy. The size and shape of the synthesized nanoparticles were characterized by infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, high-resolution transmission electron microscopy, and small-angle X-ray scattering. The average particle size was from 10 to 30?nm. Gas chromatography–mass spectrometry (GC–MS) was used for the separation, identification, and quantification of components of the plant extracts. A possible mechanism for the synthesis of nanoparticles was elucidated based on the GC–MS results. The synthesized silver nanoparticles showed effective inhibition against Streptococcus mutans, which is the main causative agent for dental caries. The nanoparticles also showed promising antibiofilm activity by inhibiting the glucosyltransferase enzyme.