Correlation Between Segmental Dynamics,Glass Transition,and Lithium Ion Conduction in Poly(Methyl Methacrylate)/Ionic Liquid Mixture

A solid-state membrane of a polymer/ionic liquid miscible mixture, poly(methyl methacrylate) (PMMA) and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆) doped with lithium perchlorate (LiClO₄), was prepared and characterized. Miscibility, segmental dynamics, glass transition and ionic conductivity were investigated. Based on the results from differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA), the system is fully miscible and of single phase. Broadening of the glass transition was observed when increasing the amount of ionic liquid, which can be attributed to mobility and flexibility differences between the polymer and ionic liquid. A large dynamical asymmetry and intrinsic mobility difference allow segmental and structural motion/relaxation over a wider temperature range by increasing the amount of ionic liquid. Saturation recovery spin–lattice relaxation time (T₁) versus temperature obtained from ⁷Li nuclear magnetic resonance (NMR) showed high mobility of lithium ions, which was almost temperature independent. Lithium ion conductivity significantly increases with increasing ionic liquid amount. It is concluded that lithium ion mobility and its conduction is positively correlated to segmental dynamics of ion carriers in this model system, which is more noticeable in mixtures with higher amounts of the ionic liquid.     

Optical and structural properties of nanocrystalline PbS thin film grown by CBD on Si(1 0 0) substrate

PbS nanocrystalline thin film was prepared by chemical bath deposition on Si(1?0?0) substrate at bath temperatures of 25, 45 and 65 °C. Triethanolamine was added to the aqueous solution, which decreased the grain size and increased the luminescence of the nanocrystalline PbS thin film. PbS nanocrystals were identified using XRD, TEM and AFM. The crystalline size of the PbS film deposited at different bath temperatures was estimated by XRD and TEM to be 7–12 nm. The growth mechanism of the PbS crystallites were described at different bath temperatures. The confinement was reflected in the absorption spectra, photoluminescence excitation and photoluminescence spectra. The luminescence of Si(1?0?0) substrate and PbS nanocrystalline film deposited on Si(1?0?0) were compared, and the results revealed that the PbS nanocrystals altered and notably enhanced the emission features of the Si(1?0?0) substrate. The shifting of the maximum photoluminescence emission wavelength of PbS nanocrystals with a change in bath temperature and the variation in photoluminescent intensity of PbS nanocrystals prepared at 25 °C versus deposition time were investigated. A single-peak fit of a Gaussian function was employed to discern the photoluminescence of PbS on Si(1?0?0) substrate.     

Using magnetic core‐shell nanoparticles coated with an ionic liquid dispersion assisted by effervescence powder for the micro‐solid‐phase extraction of four beta blockers from human plasma by ultra high performance liquid chromatography with mass spectrometry detection

In this work, a novel, efficient, and green sorbent, SiO₂@Fe₃O₄ has been created and functionalized with 1‐butyl‐3‐methylimidazolium hexafluorophosphate as an ionic liquid. This sorbent was applied for microextraction of four beta blockers, propranolol, metoprolol, atenolol, and alprenolol with bupivacaine as internal standard from human plasma followed by liquid chromatography with mass spectrometric detection. A mixture of sodium bicarbonate and sodium dihydrogen phosphate was used as an extractant dispersive agent (effervescent power) to enhance the interaction between the magnetic sorbent and analytes. Main affecting parameters on microextraction and elution were optimized. Figures of merit for dispersive solid phase extraction with ionic liquid coated magnetic nanoparticles assisted by effervescent powder were calculated under the optimized conditions. The detection limits for propranolol, metoprolol, atenolol, and alprenolol were found at 0.33, 0.62, 0.03, and 0.44 ng/mL, respectively. For all analytes, good linearity was obtained. Intra‐ (n = 5) and interday (n = 10) precision were both under 6.3% while the preconcentration factors were obtained in the range between 15–18. The extraction efficiencies for each analyte ranged from 75 to 91%. The method was successfully applied for determination of trace amounts of the beta blockers in human plasma samples.     

Synthesis of nano‐sized magnetite mesoporous carbon for removal of Reactive Yellow dye from aqueous solutions

In this study, core‐shell structures of magnetite nanoparticles coated with CMK‐8 ordered mesoporous carbon (Fe₃O₄@SiO₂‐CMK‐8 NPs) have been successfully synthesized for the first time by carbonizing sucrose inside the pores of the Kit‐6 mesoporous silica. The nano‐sized mesoporous particles were characterized by X‐ray diffraction, Fourier transform‐infrared spectroscopy, scanning electron microscope, dynamic light scattering, vibrating‐sample magnetometer, Brunauer–Emmett–Teller (BET) and transmission electron microscopy instruments. The obtained nanocomposite was used for removal of Reactive Yellow 160 (RY 160) dye from aqueous samples. The N₂ adsorption–desorption method (at 77 K) confirmed the mesoporous structure of synthesized Fe₃O₄@SiO₂‐CMK‐8 NPs. Also, the surface area was calculated by the BET method and Langmuir plot as 276.84 m²/g and 352.32 m²/g, respectively. The surface area, volume and pore diameter of synthesized nanoparticles (NPs) were calculated from the pore size distribution curves using the Barrett–Joyner–Halenda formula (BJH). To obtain the optimum experimental variables, the effect of various experimental parameters on the dye removal efficiency was studied using Taguchi orthogonal array experimental design method. According to the experimental results, about 90.0% of RY 160 was removed from aqueous solutions at the adsorbent amount of 0.06 g, pH 3 and ionic strength = 0.05 m during 10 min. The pseudo‐second order kinetic model provided a very good fit for the RY 160 dye removal (R² = 0.999). The Langmuir, Freundlich, Temkin and Dubinin–Radushkevich models were applied to describe the equilibrium isotherms, and the Langmuir isotherm showed the best fit to data with the maximum adsorption capacity of 62.893 mg/g. Furthermore, the Fe₃O₄@SiO₂‐CMK‐8 NPs could be simply recovered by external magnet, and exhibited recyclability and reusability for a subsequent six runs.     

A high‐order compact finite‐difference lattice Boltzmann method for simulation of steady and unsteady incompressible flows

A high‐order compact finite‐difference lattice Boltzmann method (CFDLBM) is proposed and applied to accurately compute steady and unsteady incompressible flows. Herein, the spatial derivatives in the lattice Boltzmann equation are discretized by using the fourth‐order compact FD scheme, and the temporal term is discretized with the fourth‐order Runge–Kutta scheme to provide an accurate and efficient incompressible flow solver. A high‐order spectral‐type low‐pass compact filter is used to stabilize the numerical solution. An iterative initialization procedure is presented and applied to generate consistent initial conditions for the simulation of unsteady flows. A sensitivity study is also conducted to evaluate the effects of grid size, filtering, and procedure of boundary conditions implementation on accuracy and convergence rate of the solution. The accuracy and efficiency of the proposed solution procedure based on the CFDLBM method are also examined by comparison with the classical LBM for different flow conditions. Two test cases considered herein for validating the results of the incompressible steady flows are a two‐dimensional (2‐D) backward‐facing step and a 2‐D cavity at different Reynolds numbers. Results of these steady solutions computed by the CFDLBM are thoroughly compared with those of a compact FD Navier–Stokes flow solver. Three other test cases, namely, a 2‐D Couette flow, the Taylor's vortex problem, and the doubly periodic shear layers, are simulated to investigate the accuracy of the proposed scheme in solving unsteady incompressible flows. Results obtained for these test cases are in good agreement with the analytical solutions and also with the available numerical and experimental results. The study shows that the present solution methodology is robust, efficient, and accurate for solving steady and unsteady incompressible flow problems even at high Reynolds numbers. Copyright © 2014 John Wiley & Sons, Ltd.     

Electronic and transport properties of monolayer graphene defected by one and two carbon ad-dimers

Using density functional theory combined with non-equilibrium Green’s function method, we have investigated the electronic and transport properties of graphenes defected by one and two carbon ad-dimers (CADs), placed parallel to the graphene lattice. Addition of these CADs to graphenes creates 3D paired pentagon–heptagon defects (3D-PPHDs). The band structure, density of states (DOS), quantum conductance, projected DOS, as well as the current–voltage characteristic per graphene super-cells containing each type of 3D-PPHD are calculated. The local strain introduced to graphene by 3D-PPHDs forces the C-bonds in the dimers to hybridize in sp ³-like rather than sp ²-like orbitals, creating localized states at the center of the corresponding defect below the Fermi energy. Simulations show that the zero-bias conductances per super-cells containing defects created by one and two CADs exhibit dip about ~0.579 and ~0.253 eV below their corresponding Fermi levels, respectively. These can be attributed to the localized states around the same energy levels. Simulations also show that the enhanced carriers scatterings within the graphenes defected by the 3D-PPHDs have increased their overall resistances, as compared with the pristine graphene. Moreover, the current–voltage characteristic calculated per super-cell for each case shows that the current for those containing one and two CADs, at an applied voltage of 0.5 V, is ~5 and 13 % less than the current calculated for the pristine super-cell of the same size.     

Effect of phenolic compounds and quinones on radiation-induced oxidation processes of hexane and ethanol

The radiation-chemical yields were determined for the products of γ-radiation induced oxidation of hexane and ethanol in the presence of natural and synthetic phenolic compounds and quinones. It was found that the commercial antioxidants ionol and bisphenol 2246 more effectively inhibit the hexane oxidation process while α-tocopherol and quinones are superior to other test compounds in the suppression of ethanol oxidation. The results indicate that the antioxidant properties of phenolic compounds and quinones depend not only on their structure but also on the nature of the oxidation substrate. The cause of this phenomenon is discussed.     

Operational Matrix of Fractional Integration Based on the Shifted Second Kind Chebyshev Polynomials for Solving Fractional Differential Equations

This paper is devoted to studying a computational method for solving multi-term differential equations based on new operational matrix of shifted second kind Chebyshev polynomials. The properties of the operational matrix of fractional integration are exploited to reduce the main problem to an algebraic equation. We present an upper bound for the error in our estimation that leads to achieve the convergence rate of O(M ^−κ). Numerical experiments are reported to demonstrate the applicability and efficiency of the proposed method.