Characterization,optical, and nanoscale free volume properties of Na‐CMC/PAM/CNT nanocomposites

Polyblend and nanocomposite films of sodium salt of carboxymethylcellulose (Na‐CMC)/polyacrylamide (PAM) and Na‐CMC/PAM modified with carbon nanotubes (CNT) were synthesized by the solution casting technique. The effect of PAM and CNT loading on the structural, optical, and nanoscale free volume properties of Na‐CMC was studied. X‐ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy exhibited the existence of strong interactions between Na‐CMC and PAM and the non‐destructive effect of CNT on Na‐CMC/PAM structure. The HR‐TEM revealed the multi‐walled structure of CNT with a 7.06‐nm wall thickness and a 6.92‐nm wall inner diameter. Positron annihilation lifetime spectroscopy (PALS) was done, in a vacuum and at 30°C to 200°C, to investigate the nanoscale free volume properties by using a conventional fast‐fast coincidence spectrometer. It was found that the o‐Ps lifetime (τ₃ ) and free volume (V_h) increase with increasing CNT percentage in the Na‐CMC/PAM blend. The distribution of the o‐Ps lifetime was broadened with increasing CNT ratios. Furthermore, the glass transition temperature (T_g) increases with increasing loads of CNT. For the first time, a correlation was done between Urbach energy (E_U) and V_h. Finally, the results were represented and discussed in the frame of free volume properties. Optical measurements showed that the transmittance T% of Na‐CMC/PAM was 91.12% and decreased to 68.42% and 36.45% after loading with 1.0 and 2.0 wt % CNT. In addition, the blend shows higher insulating properties compared with the individual polymers. The CNT incorporation reduces the band gap significantly and increases the E_U in the films.     

Low temperature phases of the Andelman-de Gennes model of chiral discrimination: rigorous results

We determine the ordered low temperature phases of the Andelman-de Gennes model of chiral discrimination, using rigorous statistical mechanical methods. The system is considered in the close-packed regime, equivalent to placing the molecules at every site of a honeycomb lattice. If the system contains an equimolar mixture of each of a pair of enantiomers, we prove in general that a heterochiral phase (disfavoring enantiomeric segregation) as well as a homochiral phase (favoring the segregation) is possible, depending on the types of intermolecular interactions. We apply our general results to the specific examples of the interactions considered by Andelman and de Gennes and provide a comparison with their conjectures that were based on two-molecule partition functions.     

Extending the eigCG algorithm to nonsymmetric Lanczos for linear systems with multiple right‐hand sides

The technique that was used to build the eigCG algorithm for sparse symmetric linear systems is extended to the nonsymmetric case using the BiCG algorithm. We show that, similar to the symmetric case, we can build an algorithm that is capable of computing a few smallest magnitude eigenvalues and their corresponding left and right eigenvectors of a nonsymmetric matrix using only a small window of the BiCG residuals while simultaneously solving a linear system with that matrix. For a system with multiple right‐hand sides, we give an algorithm that computes incrementally more eigenvalues while solving the first few systems and then uses the computed eigenvectors to deflate BiCGStab for the remaining systems. Our experiments on various test problems, including Lattice QCD, show the remarkable ability of eigBiCG to compute spectral approximations with accuracy comparable with that of the unrestarted, nonsymmetric Lanczos. Furthermore, our incremental eigBiCG followed by appropriately restarted and deflated BiCGStab provides a competitive method for systems with multiple right‐hand sides. Copyright © 2013 John Wiley & Sons, Ltd.     

Optimal design of 32 channels spectrum slicing WDM for optical fiber access network system

In this article, the spectrum sliced dense wavelength division multiplexed passive optical network (SS-DWDM–PON) has been investigated as a power efficient and cost effective solution for optical access networks. In this work an AWG demultiplexer is used to operate as slicing system. The high speed SS-DWDM system has been realized and investigated for 32 channels with data rate up to 3 Gb/s using broadband ASE source (LED). The 3 Gb/s signals both non-return-to-zero (NRZ) and return-to-zero (RZ) were demonstrated in 40 km optical fiber link with BER < 10⁻¹². The results obtained here demonstrate that SS-DWDM is well suited for Fiber-to-the-Home (FTTH) network.     

Characterization of mediastinal lymphadenopathy with diffusion-weighted imaging

Purpose

To predict malignancy of mediastinal lymphadenopathy with diffusion-weighted imaging.

Material and methods

A prospective study was conducted on 35 patients with mediastinal lymphadenopathy (28 malignant and seven benign nodes). They underwent echoplanar diffusion-weighted magnetic resonance imaging of the mediastinum with b-factors of 0, 300 and 600 s/mm². The apparent diffusion coefficient (ADC) values of the mediastinal lymph nodes were calculated. The ADC values were correlated with the biopsy results and statistical analysis was done. A value of P<.05 was considered significant.

Results

The mean ADC value of malignant mediastinal lymphadenopathy (1.06±0.3×10⁻³ mm²/s) was significantly lower (P=.001) than that of benign lymphadenopathy (2.39±0.7×10⁻³ mm²/s). There was an insignificant difference in the ADC values between metastatic and lymphomatous mediastinal lymph nodes (P=.32) as well as within benign nodes (P=.07). When an ADC value of 1.85×10⁻³ mm²/s was used as a threshold value for differentiating malignant mediastinal nodes from benign nodes, the best results were obtained with an accuracy of 83.9%, a sensitivity of 96.4%, a specificity of 71.4%, a negative predictive value of 95.2% and a positive predictive value of 77.1%. The area under the curve was 0.98.

Conclusion

Diffusion weighted magnetic resonance imaging is a promising noninvasive imaging modality that can be used for characterization of mediastinal lymphadenopathy and differentiation of malignant from benign mediastinal lymph nodes.     

Magnetic and binding properties of metal-divacancy complexes at MgO (0 0 1) surface: DFT calculations

We have analyzed the magnetic and binding properties of Ni, Cr, Mo, and Pt metals deposited on the defect free and defect containing surfaces of MgO by means of density functional theory calculations and embedded cluster model. Clusters of moderate sizes with no border anions, to avoid artificial polarization effects, were embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces. Spin quenching occurs for Cr and Mo complexes at the defect free (terrace) surface, and Cr, Mo, and Pt complexes at the defect containing “pit” divacancy surface. The binding energies of the metals are significantly enhanced on the cationic vacancy end of the divacancy. The adsorption energies of the low spin states of spin quenched complexes are always greater than those of the high spin states. The metal-support interactions stabilize the low spin states of the adsorbed metals with respect to the isolated metals, but the effect is not always enough to quench the spin. The encountered variations in magnetic properties of free metals and of metal complexes are correlated with the energy gaps of the frontier orbitals. Spin contamination affect the adsorbate-substrate distances, Mulliken charges, Mulliken spin densities, natural charge, natural orbital population, and provide rationalization for the reported magnetic and binding properties. The electrostatic potential energy curves provide clearer understanding of the nature of magnetic and binding interactions. The magnetic and binding properties of a single metal atom adsorbed on a particular surface result from a competition between Hund's rule for the adsorbed metal, and the formation of a chemical bond at the interface.     

Numerical simulation of the interface molten metal air in the shot sleeve chambre and mold cavity of a die casting machine

The objective of this study relates to the numerical simulation of the free surface during the two-dimensional flow and solidification of aluminum in the horizontal cylinder and mold cavity of the high pressure die casting HPDC machine with cold chamber. The flow is governed by the Navier–Stokes equations (the mass and the momentum conservations) and solved in the two phase’s liquid aluminum and air. The tracking of the free surface is ensured by the VOF method. The equivalent specific heat method is used to solve the phase change heat transfer problem in the solidification process. Considering the displacement of the plunger, the geometry of the problem is variable and the numerical resolution uses a dynamic grid. The study examines the influence of the plunger speed on the evolution of the interface aluminum liquid–air profile, the mass of air imprisoned and the stream function contours versus time. Filling of a mold is an essential part of HPDC process and affects significantly the heat transfer and solidification of the melt. For this reason, accurate prediction of the temperature field in the system can be achieved only by including simulation of filling in the analysis.     

Time-dependent radiolytic yield of OH• radical studied by picosecond pulse radiolysis

Picosecond pulse radiolysis measurements using a pulse-probe method are performed to measure directly the time-dependent radiolytic yield of the OH(?) radical in pure water. The time-dependent absorbance of OH(?) radical at 263 nm is deduced from the observed signal by subtracting the contribution of the hydrated electron and that of the irradiated empty fused silica cell which presents also a transient absoption. The time-dependent radiolytic yield of OH(?) is obtained by assuming the yield of the hydrated electron at 20 ps equal to 4.2 × 10(-7) mol J(-1) and by assuming the values of the extinction coefficients of e(aq)(-) and OH(?) at 782 nm (ε(λ=782 nm) = 17025 M(-1) cm(-1)) and at 263 nm (ε(λ=263 nm) = 460 M(-1) cm(-1)), respectively. The value of the yield of OH(?) radical at 10 ps is found to be (4.80 ± 0.12) × 10(-7) mol J(-1).     

Intermolecular hydrogen bond complexes by in situ charge transfer complexation of o-tolidine with picric and chloranilic acids

A two new charge transfer complexes formed from the interactions between o-tolidine (o-TOL) and picric (PA) or chloranilic (CA) acids, with the compositions, [(o-TOL)(PA)(2)] and [(o-TOL)(CA)(2)] have been prepared. The (13)C NMR, (1)H NMR, (1)H-Cosy, and IR show that the charge-transfer chelation occurs via the formation of chain structures O-H?N intermolecular hydrogen bond between 2NH(2) groups of o-TOL molecule and OH group in each PA or CA units. Photometric titration measurements concerning the two reactions in methanol were performed and the measurements show that the donor-acceptor molar ratio was found to be 1:2 using the modified Benesi-Hildebrand equation. The spectroscopic data were discussed in terms of formation constant, molar extinction coefficient, oscillator strength, dipole moment, standard free energy, and ionization potential. Thermal behavior of both charge transfer complexes showed that the complexes were more stable than their parents. The thermodynamic parameters were estimated from the differential thermogravimetric curves. The results indicated that the formation of molecular charge transfer complexes is spontaneous and endothermic.     

Molecular spectroscopic analyses of gelatin

The molecular structure of gelatin was studied using Fourier transform infrared spectroscopy FTIR. The spectrum is subjected to deconvolution in order to elucidate the constituents of the molecular structure. B3LYP/6-31g** was used to study 13 amino acids then the scaled spectrum was compared to those of protein in order to describe the contribution of each amino acid into protein structure. A special interest was paid to the NH and C=O region. The reactivity of each amino acid was studied in terms of some important physical parameters like total dipole moment and HOMO/LUMO which describe the interaction of amino acid with their surrounding molecules. Results indicated that B3LYP/6-31g** model is a suitable and precise method for studying molecular structure of protein.