Structure–reactivity studies of chloro and isothiocyanato diorganotin (IV) complexes based on multidentate N‐donor ligands: Synthesis,spectral characterization and crystal structures

The reaction of [SnMe₂Cl₂] with the bidentate ligand 4,7‐phenanthroline (4,7‐phen) resulted in the formation of [SnMe₂Cl₂ (4,7‐phen)]_n ( 1a ) which is probably a polymeric chain in solution. On the other hand, the reaction of [SnEt₂Cl₂] with 4,7‐phen afforded the complex [Sn₂Et₄Cl₄ (κ¹‐N‐4,7‐phen)₂(μ‐κ²‐N,N‐4,7‐phen)] ( 1b ) which dissociates in dimethylsulfoxide solution. The reaction of [SnR₂Cl₂] (R = Me, Et) with 2,2′‐biquinoline (biq) yielded the complexes [SnMe₂Cl₂ (κ²‐N,N‐biq)] ( 2a ) and [SnEt₂Cl₂ (κ¹‐N‐biq)₂] ( 2b ) in the solid state. Moreover, the reaction of [SnR₂Cl₂] (R = Me, Et) with the tridentate ligand 4′‐(2‐furyl)‐2,2′:6′,2″‐terpyridine (ftpy) resulted in the formation of ionic penta‐ and hexa‐coordinated tin complexes [SnMe₂Cl (ftpy)][SnMe₂Cl₃] ( 3a ) and [SnEt₂Cl (ftpy)]Cl ( 3b ). The reaction of [SnMe₂ (NCS)₂] with ftpy afforded the hepta‐coordinated complex [SnMe₂ (NCS)₂(ftpy)] ( 4a ). The products were fully characterized using elemental analysis, and infrared, UV–visible, multinuclear (¹H, ¹³C, ¹¹⁹Sn) NMR, DEPT‐135°, HH‐COSY and HSQC NMR spectroscopies. The crystal structure of complex 3a reveals that it contains the simultaneous presence of penta‐ and hexa‐coordinated tin (IV) atoms. Notably, the crystal structure of complex 4a shows that tin (IV) is hepta‐coordinated in a pentagonal bipyramidal geometry SnC₂N₅ by three nitrogen atoms of ftpy, two nitrogen atoms of NCS^? and two Me groups with trans‐[SnMe₂] configuration. These data indicate the influence of halide or pseudo‐halide group on the coordination number and geometry of tin. Hirshfeld surface analysis and two‐dimensional fingerprint plots were calculated for 3a and 4a which show the π–π interaction between molecules in the solid is relatively weak.     

Rheological and Mechanical Characterization of Multi-Walled Carbon Nanotubes/Polypropylene Nanocomposites

The rheology and morphology of multi-walled carbon nanotube (MWNT)/polypropylene (PP) nanocomposites prepared via melt blending was investigated. The minor phase content of MWNT varied between 0.25 and 8 wt%. From morphological studies using a scanning electron microscopy technique a good dispersion of carbon nanotubes in the PP matrix was observed. The rheological studies were performed by a capillary rheometer, and mechanical properties of the nanocomposites were studied using a tensile and flexural tester. Both PP and its nanocomposites showed non-Newtonian behavior. At low shear rates the addition of MWNT content causes an increase in viscosity; however, viscosity is less sensitive to addition of MWNT content at higher shear rates. Flow activation energy for the nanocomposites was calculated using an Arrhenius type equation. From this calculation it was concluded that the temperature sensitivity of nanocomposites was increased by increasing of nanotube content. An increase in tensile and flexural moduli and Izod impact strength was also observed by increasing the MWNT content. From rheological and mechanical tests it was concluded that the mechanical and rheological percolation threshold is at 1.5 wt%.     

A novel algorithm based on parameterization method for calculation of curvature of the free surface flows

In this paper, a new approach based on parameterization method is presented for calculation of curvature on the free surface flows. In some phenomena such as droplet and bubble, surface tension is prominent. Therefore in these cases, accurate estimation of the curvature is vital. Volume of fluid (VOF) is a surface capturing method for free surface modeling. In this method, free surface curvature is calculated based on gradient of scalar transport parameter which is regarded as original method in this paper. However, calculation of curvature for a circle and other known geometries based on this method is not accurate. For instance, in practice curvature of a circle in interface cells is constant, while this method predicts different curvatures for it. In this research a novel algorithm based on parameterization method for improvement of the curvature calculation is presented. To show the application of parameterization method, two methods are employed. In the first approach denoted by, three line method, a curve is fitted to the free surface so that the distance between curve and linear interface approximation is minimized. In the second approach namely four point method, a curve is fitted to intersect points with grid lines for central and two neighboring cells. These approaches are treated as calculus of variation problems. Then, using the parameterization method, these cases are converted into the sequences of time-varying nonlinear programming problems. With some treatments a conventional equivalent model is obtained. It is finally proved that the solution of these sequences in the models tends to the solution of the calculus of variation problems. For verification of the presented methods, curvature of some geometrical shapes such as circle, elliptic and sinusoidal profile is calculated and compared with original method used in VOF process and analytical solutions. Finally, as a more practical problem, spurious currents are studied. The results showed that more accurate curve prediction is obtained by these approaches than the original method in VOF approach.     

Synthesis,biological evaluation and molecular docking study of dihydropyrimidine derivatives as potential anticancer agents

A series of dihydropyrimidine analogues were prepared via one-pot Biginelli three-component condensation reaction and characterized by NMR, FT-IR, MS spectra, and element analysis. Subsequently, they were screened for in vitro anticancer effect. These analogues revealed good cytotoxic activity against three human cancer cell lines including MCF-7, HepG-2, and A549. Among these analogues, compounds 4d and 4h were the most potent against three cell lines. Cell viability assays indicated 4a and 4c had lower cytotoxicity. In vitro cytotoxicity study on all synthesized compounds demonstrated that introduction of electron withdrawing substituents on C4 position of phenyl ring of dihydropyrimidine contributed to the antiproliferative potency. Moreover, in silico molecular docking results stipulated a sign of good correlation between experimental activity and calculated binding affinity. It proved 4d and 4h as the strongest compounds. Binding modes of analogues proposed the involvement of hydrophobic interactions and hydrogen bonds with Eg5 active site. Structure activity relationship studies indicated that incorporating electron withdrawing substituents on C4 position of phenyl ring of dihydropyrimidine are important for this biological activity.     

Nonlinear Dynamics of Circularly Polarized Laser Pulse Propagating in a Magnetized Plasma with q ‐Nonextensive Velocity Distributions

The nonlinear dynamics of a circularly polarized laser pulse propagating in magnetized plasma contains hot nonextensive q ‐distributed electrons and ions is studied theoretically. A nonlinear equation which describes the dynamics of the slowly varying amplitude electromagnetic wave is obtained using the relativistic two‐fluids model. Some nonlinear phenomena include modulational instability, self‐focusing, soliton formation, and longitudinal and transversal evolutions of laser pulse in nonextensive plasma medium are investigated. Results show that the nonextensivity of particles can substantially change the nonlinearity of medium. The external magnetic field enhances the modulation instability growth rate of right‐hand polarization wave but for the left‐hand polarization the growth rate decreases. The spot size of the laser pulse is strongly affected by the plasma nonextensivity. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectroscopic studies of dehydrogenation of ammonia borane in carbon cryogel

Ammonia borane (AB) is of great interest for storing hydrogen, an important issue in the growing field of hydrogen technology. The reaction pathways leading to the thermal decomposition of solid-state AB incorporated in carbon cryogels (CC) have been studied by spectroscopic methods. The time-dependent thermal decomposition was followed by in situ 11B nuclear magnetic resonance (NMR) and showed a significant increase in hydrogen release kinetics for AB in CC compared to neat AB. Both 11B NMR and Fourier transform infrared spectroscopy show a new reaction product, formed in the thermal decomposition of AB in CC scaffold (CC-AB) that is assigned to reactions with surface oxygen groups. The results indicate that incorporation of AB in CC enhances kinetics because of the reactions with residual surface-bound oxygen functional groups. The formation of new products with surface -O-B bonds is consistent with the greater reaction exothermicity observed when hydrogen is released from CC-AB materials. Scanning electron microscopy shows different morphology of AB in CC-AB nanocomposite as compared to neat AB.     

Coherent carbon cryogel-ammonia borane nanocomposites for H2 storage

Coherent carbon cryogel-ammonia borane (C-AB) nanocomposites were synthesized, and improved H2 storage properties are reported. Porous carbon cryogels were impregnated with AB in tetrahydrofuran solution at 25 degrees C under argon; 30% of the carbon cryogel pore volume was filled to produce a 24 wt % C-AB nanocomposite. Nitrogen sorption isotherms, X-ray diffraction, differential scanning calorimetry, differential thermal/thermal gravimetric analyses, mass spectrometry, and 11B NMR were used to characterize the coherent C-AB nanocomposites. Findings include a merged two-step hydrogen release reaction with an appreciable reduction in the dehydrogenation temperature to <90 degrees C as well as the suppression of borazine release. The possible nanosize effects on the H2 storage properties are discussed.     

Electromagnetically Induced Transparency of Two Intense Circularly-Polarized Lasers in Cold Plasma: Beat-Wave Second Harmonic Effect

In the present paper the problem of nonlinear interaction of two mildly-relativistic circularly polarized lasers in a cold plasma is studied in order to investigate electromagneticaily induced transparency （EIT）. Based on a relativistic kinetic model, by expansion of relativistic Lorentz factor in terms of lasers amplitude, we obtain the coupled nonlinear dispersion relations. It is observed that due to resonance in the second harmonic of plasma beat-wave, the new EIT pass-band is created in the high intensities of lasers. The effect of amplitude and frequency variation on the dispersion is numerically investigated.     

Three-dimensional characterization of multiply twinned nanoparticles by high-angle tilt series of lattice images and tomography

A new electron tomography methodology is presented which allows the reconstruction of external particle shape from lattice resolved high-resolution electron microscopy images. The technique is based on the shape-from-silhouette binary backprojection algorithm after filtering of the lattice contrast. The simultaneous availability of particle shape and crystallographic lattice plane orientations allows the correlation of faceting with crystallographic orientations. The method is demonstrated using a multiply twinned decahedral gold nanoparticle. Eligibility limits in terms of degree of convexity are derived.