Colossal Stability of SiB11(BO)12−: An Implication as Potential Electrolyte in High-Voltage Alkali-ion Battery

High-voltage alkali metal-ion batteries (AMIBs) require a non-hazardous, low-cost, and highly stable electrolyte with a large operating potential and rapid ion conductivity. Here, we have reported a halogen-free high-voltage electrolyte based on SiB₁₁(BO)₁₂⁻. Because of the weak π-orbital interaction of −BO as well as the mixed covalent and ionic interaction between SiB₁₁-cage and −BO ligand, SiB₁₁(BO)₁₂⁻ has colossal stability. SiB₁₁(BO)₁₂⁻ possesses extremely high vertical detachment energy (9.95 eV), anodic voltage limit (∼10.05 V), and electrochemical stability window (∼9.95 V). Furthermore, SiB₁₁(BO)₁₂⁻ is thermodynamically stable at high temperatures, and its large size allows for faster cation movement. The alkali salts MSiB₁₁(BO)₁₂ (M=Li, Na, and K) are easily dissociated into ionic components. Electrolytes based on SiB₁₁(BO)₁₂⁻ greatly outperform commercial electrolytes. In short, SiB₁₁(BO)₁₂⁻-based compound is demonstrated to be a high-voltage electrolyte for AMIBs.     

UV light-assisted mineralisation and biodetoxification of Ponceau S with hydroxyl and sulfate radicals

The present study reports simultaneous mineralisation and biodetoxification of Ponceau S (3-hydroxy-4-(2-sulfo-4-[4-sulfophenylazo]phenylazo)-2,7-naphthalenedisulfonic acid sodium salt), an azo dye, by UV light assisted oxidation with hydroxyl and sulfate radicals. Metal ion catalysts used in the work were: Fe²⁺ and Ag⁺, and the oxidants used were: hydrogen peroxide and S₂O₈^2?. Strategies adopted to make the processes environmentally benign and economically viable by achieving maximum mineralisation in the shortest possible time are described. Mineralisation efficiency (Em) of various systems was found to follow the order: E_m(Fe²⁺/H₂O₂/UV) > E_m(Fe²⁺/S₂O₈^2?/UV) > E_m(Ag⁺/H₂O₂/UV) ≈ E_m(Ag⁺/S₂O₈^2?/UV). Thus, Fe²⁺ and HP are the most suitable metal ion catalyst and oxidant respectively, showing higher efficiency at pH 3 followed by that at pH 6.6. It is possible to enhance the Fe²⁺/H₂O₂/UV process electrical energy efficiency by maintaining the concentration of Fe at either 0.05 mM or 0.03 mM and that of the oxidant at 2.5 mM. The bioassay study revealed that the Fe²⁺/S₂O₈^2?/UV process biodetoxification efficiency is higher at pH 3 (93.7 %) followed by that at pH 6.6 (80.1 %) at the concentration of Fe ²⁺ and S₂O₈^2? of 0.03 mM and 2.5 mM, respectively. Thus, not only the concentration of Fe²⁺, but also the nature of the oxidant and pH play an important role in the biodetoxification process and S₂O₈^2? possesses higher biodetoxification efficiency than H₂O₂.     

CPMD/GULP QM/MM interface for modeling periodic solids: Implementation and its application in the study of Y‐zeolite supported Rhn clusters

We report here the development of hybrid quantum mechanics/molecular mechanics (QM/MM) interface between the plane‐wave density functional theory based CPMD code and the empirical force‐field based GULP code for modeling periodic solids and surfaces. The hybrid QM/MM interface is based on the electrostatic coupling between QM and MM regions. The interface is designed for carrying out full relaxation of all the QM and MM atoms during geometry optimizations and molecular dynamics simulations, including the boundary atoms. Both Born–Oppenheimer and Car–Parrinello molecular dynamics schemes are enabled for the QM part during the QM/MM calculations. This interface has the advantage of parallelization of both the programs such that the QM and MM force evaluations can be carried out in parallel to model large systems. The interface program is first validated for total energy conservation and parallel scaling performance is benchmarked. Oxygen vacancy in α‐cristobalite is then studied in detail and the results are compared with a fully QM calculation and experimental data. Subsequently, we use our implementation to investigate the structure of rhodium cluster (Rh_n; n = 2 to 6) formed from Rh(C₂H₄)₂ complex adsorbed within a cavity of Y‐zeolite in a reducible atmosphere of H₂ gas. © 2016 Wiley Periodicals, Inc.     

A 10-A spectroscopic ruler applied to short polyprolines

Fluorescence resonance energy transfer (FRET) from the amino acid tryptophan (Trp) as donor and a 2,3-diazabicyclo[2.2.2]oct-2-ene-labeled asparagine (Dbo) as acceptor in peptides of the general structure Trp-(Pro)n-Dbo-NH2 (n = 1-6) was investigated by steady-state and time-resolved fluorescence, CD, and NMR spectroscopy as well as by molecular dynamics (MD) simulations (GROMOS96 force field). The Trp/Dbo FRET pair is characterized by a very short F?rster radius (R0 ca. 9 A), which allowed distance determinations in such short peptides. Water and propylene glycol were investigated as solvents. The peptides were designed to show an early nucleation of the poly(Pro)II (PPII) secondary helix structure for n > or = 2, which was confirmed by their CD spectra. The shortest peptide (n = 1) adopts preferentially the trans conformation about the Trp-Pro bond, as confirmed by NMR spectra. The FRET efficiencies ranged 2-72% and were found to depend sensitively on the peptide length, i.e., the number of intervening proline residues. The analysis of the FRET data at different levels of theory (assuming either a fixed distance or distance distributions according to a wormlike chain or Gaussian model) afforded donor-acceptor distances between ca. 8 A (n = 1) and ca. 16 A (n = 6) in water, which were found to be similar or slightly higher in propylene glycol. The distances afforded by the Trp/Dbo FRET pair were found to be reasonable in comparison to literature data, expectations from the PPII helix structure, and the results from MD simulations. The persistence lengths for the longer peptides were found to lie at 30-70 A in water and 220 +/- 40 A in propylene glycol, suggesting a more rigid PPII helical structure in propylene glycol. A detailed comparison with literature data on FRET in polyprolines demonstrates that the donor-acceptor distances extracted by FRET are correlated with the F?rster radii of the employed FRET pairs. This demonstrates the limitations of using FRET as a spectroscopic ruler for short polyprolines, which is presumably due to the breakdown of the point dipole approximation in F?rster theory, when the size of the chromophores becomes comparable or larger than the distances under investigation.     

Computational modeling of heat transfer and sintering behavior during direct metal laser sintering of AlSi10Mg alloy powder

Direct Metal Laser Sintering (DMLS) is one of the leading additive manufacturing processes, which produces complex metallic parts directly from the powder. One of the major problems of this rapid manufacturing process is an inhomogeneous temperature distribution, which leads to residual stress in the build part. Thus, temperature analyses must be performed, to better understand the temperature distribution and sintering behavior of the powder bed with a different laser recipe. In this study, a comprehensive three-dimensional numerical model was developed to understand the temperature distribution during direct metal laser sintering of AlSi10Mg alloy powder. The computer simulation was carried out in ANSYS 17.0 platform. Further, the effect of process parameters such as laser power and scan speed on the temperature distribution and sintering behavior were studied. From the simulation results, it was found that, when the laser power increased from 70 W to 190 W, the maximum temperature of the molten pool increased from 731?°C to 2672?°C, and the molten pool length changed from 0.286 mm to 2.167 mm. A reverse phenomenon was observed with an increase in scan speed. The sintering depth of the powder layer increases significantly from 0.061 mm to 0.872 mm with increasing the applied laser power, but decreased from 0.973 mm to 0.209 mm as a higher scan speed was applied. The developed model helps to optimize the powder layer thickness and minimize the wastage of excess powders during the sintering process.     

New double-periodic solutions of fractional Drinfeld–Sokolov–Wilson equation in shallow water waves

Nonlinear Dynamics - In the present article, the new exact solutions of time-fractional coupled Drinfeld–Sokolov–Wilson equations have been derived by using a new reliable analytical...     

Natural Convection Heat Transfer Augmentation Factor with Square Conductive Pin Fin Arrays

Natural convection heat transfer from a vertical isothermal plate with pin fins is numerically studied by solving the Navier–Stokes equations along with the energy equation. The average Nusselt number for the plate with different configurations of pin fins is obtained. The average Nusselt number is found to increase with increasing aspect ratio of the fin and to decrease with increasing angle of fin inclination with respect to the plate. There is only a minor difference between the average Nusselt numbers for in-line and staggered arrangement of fins for the range of parameters studied in the present work. A correlation is developed to predict the average Nusselt number of the plate as a function of fin spacing in the streamwise and spanwise directions, aspect ratio of the fin, and its angle of inclination.     

Hydroelastic analysis of very large floating structure over viscoelastic bed

Effect of viscoelastic bed on the hydroelastic response analysis of very large floating structures is studied using the linear water wave theory and small amplitude structural response in finite water depth. The floating structure is modeled using Euler–Bernoulli beam equation and the bottom bed is assumed to be viscoelastic in nature and is based on the Voigt’s model. The dispersion relation, phase speed and response amplitude of the floating structure as well as viscoelastic bed surface, pressure distribution along water depth are analyzed to study the effect of viscoelastic bed parameters, flexural rigidity of the floating structure, time period on flexural gravity wave motion. The study reveals that structural response of the floating structure can be mitigated for moderate thickness of the viscoelastic layer. Moreover, both shear modulus and viscosity of the viscoelastic layer play dominant role in reducing the structural response compared to the flexural rigidity of the structure. Further, pressure distribution within the viscoelastic bed decreases at a higher rate compared to the inviscid fluid layer irrespective of shear modulus and viscosity. The present study will be of immense help in the site selection of very large floating structures in the coastal water and installation of various marine facilities over muddy bed.     

New Exact Solutions of Fractional Zakharov–Kuznetsov and Modified Zakharov–Kuznetsov Equations Using Fractional Sub-Equation Method

In the present paper, we construct the analytical exact solutions of some nonlinear evolution equations in mathematical physics; namely the space-time fractional Zakharov–Kuznetsov(ZK) and modified Zakharov–Kuznetsov(m ZK) equations by using fractional sub-equation method. As a result, new types of exact analytical solutions are obtained. The obtained results are shown graphically. Here the fractional derivative is described in the Jumarie's modified Riemann–Liouville sense.     

Phonon confinement and substitutional disorder in Cd1−xZnxS nanocrystals

1‐longitudinal optical (LO) phonons in free‐standing mixed Cd_1−xZn_xS nanocrystals, synthesized using chemical precipitation, are investigated using Raman spectroscopy. As expected for the nanocrystals, the 1‐LO modes are found to appear at slightly lower wavenumbers than those in the bulk mixed crystals and exhibit one‐mode behavior. On the other hand, the line broadening is found to be much more than that can be accounted on the basis of phonon confinement. From the detailed line‐shape analysis it turns out that the substitutional disorder in the mixed crystals contributes much more to the line broadening than the phonon confinement. The linewidth arising from these mechanisms are also extracted from the analysis. Copyright © 2009 John Wiley & Sons, Ltd.