The polyoxometallate [(CH3)4N]2[Mo4O10(OCH3)4Cl2]

The crystal and molecular structure of bis(tetra­methyl­ammonium) di­chloro­tetra‐μ₂‐methoxo‐di‐μ₂‐oxo‐octo­oxo­tetra­molybdate(VI), (C₄H₁₂N)₂[Mo₄O₁₀(OCH₃)₄Cl₂], has been determined from X‐ray diffraction data. The crystallographically centrosymmetric anion is built up of four edge‐sharing octahedra, two MoO₆ and two MoO₅Cl.     

Simulation of Electronic Circular Dichroism of Nucleic Acids: From the Structure to the Spectrum

We present a quantum mechanical (QM) simulation of the electronic circular dichroism (ECD) of nucleic acids (NAs). The simulation combines classical molecular dynamics, to obtain the structure and its temperature‐dependent fluctuations, with a QM excitonic model to determine the ECD. The excitonic model takes into account environmental effects through a polarizable embedding and uses a refined approach to calculate the electronic couplings in terms of full transition densities. Three NAs with either similar conformations but different base sequences or similar base sequences but different conformations have been investigated and the results were compared with experimental observations; a good agreement was seen in all cases. A detailed analysis of the nature of the ECD bands in terms of their excitonic composition was also carried out. Finally, a comparison between the QM and the DeVoe models clearly revealed the importance of including fluctuations of the excitonic parameters and of accurately determining the electronic couplings. This study demonstrates the feasibility of the ab initio simulation of the ECD spectra of NAs, that is, without the need of experimental structural or electronic data.     

A multiscale approach to thermoplastic deformation

The paper applies a multiscale formulation to thermoplasticity problems. The plasticity model is based on the variationally consistent formulation at the micro level. It is suitable for problems involving large strains. The temperature field is calculated at the macro level and is assumed to be homogeneous at the micro level. The proposed formulation is implemented in the Abaqus software by means of user subroutines. User subroutines are introduced both at the macro and at the micro level. The consistent tangent operator is calculated by the numerical differentiation procedure. Implementation details are briefly addressed. Finally, the methodology is verified on a representative example and relevant results are presented and discussed. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Contact value relations and density functional theory for the electrical double layer

The recently developed contact-corrected density functional theory is applied to an electric double layer containing a valence and size symmetric electrolyte. The restricted primitive model is used to describe the electrolyte, and a non-polarisable, smooth, planar, uniformly charged hard surface is used to model the electrode. Comparison with Monte Carlo simulation results for this system shows that the theory satisfies the first contact value relation in line with the premise of the approach. Additionally, the theory is found to satisfy the semi-empirical second contact value relation quite closely. This is a welcome result, since no reference is made to this second relation nor is the relation used in the theoretical development. The second contact relation is closely related to the anomalous positive temperature derivative of the double layer capacitance at low temperature, low ion concentration, and low electrode charge, and indeed, the contact-corrected density functional theory predicts this effect.     

An Optimal Chance Constraint Multivariate Stratified Sampling Design Using Auxiliary Information

When we are dealing with multivariate problem then we need an allocation which is optimal for all the characteristics in some sense because the individual optimum allocations usually differ widely unless the characteristics are highly correlated. So an allocation called “Compromise allocation” is to be worked out suggested by Cochran. When auxiliary information is also available, it is customary to use it to increase the precision of the estimates. Moreover, for practical implementation of an allocation, we need integer values of the sample sizes. In the present paper the problem is to determine the integer optimum compromise allocation when the population means of various characteristics are of interest and auxiliary information is available for the separate and combined ratio and regression estimates. This paper considers the optimum compromise allocation in multivariate stratified sampling with non-linear objective function and probabilistic non-linear cost constraint. The probabilistic non-linear cost constraint is converted into equivalent deterministic one by using Chance Constrained programming. The formulated multi-objective nonlinear programming problem is solved by Fuzzy Goal programming approach and Chebyshev approximation. Numerical illustration is also given to show the practical utility of the approaches.     

Synthesis and Bioactivity of Benzothiazaphosphepines and Relevant Phosphonates as Antioxidant/Antidiabetic Agents

An efficient approach to a new series of benzothiazaphosphepines and their derived phosphonates in good yields (64–75%) was reported. The strategy relied on the reactions of the easily available 2-arylmethylene-aminobenzenethiols with different types of Wadsworth–Horner–Emmons (WHE) reagents in dimethylformamide (DMF)/lithium hydride (LiH) solution. All new compounds were bioscreened and showed, in vitro, moderate to good antioxidant and antidiabetic activities.     

Dielectric and thermal effects on the optical properties of natural dyes: a case study on solvated cyanin

The optical properties of the flavylium state of the cyanin dye are simulated numerically by combining Car-Parrinello molecular dynamics and linear-response time-dependent density functional theory calculations. The spectrum of the dye calculated in the gas phase is characterized by two peaks in the yellow and in the blue (green and violet), using a GGA-PBE (hybrid-B3LYP) DFT functional, which would bring about a greenish (bright orange) color incompatible with the dark purple hue observed in nature. Describing the effect of the water solvent through a polarizable continuum model does not modify qualitatively the resulting picture. An explicit simulation of both solvent and thermal effects using ab initio molecular dynamics results instead in a spectrum that is compatible with the observed coloration. This result is analyzed in terms of the spectroscopic effects of the molecular distortions induced by thermal fluctuations.     

High‐refractive‐index and high‐barrier‐capable epoxy‐phenoxy‐based barrier film for organic electronics

A barrier film is a fundamental component of the fast growing organic electronic device industry that is necessary to sustain long‐term stability. The barrier film prevents the permeation of environmental moisture and oxygen into the organic electronic device. Superior barrier property is the most crucial characteristic of a barrier film, in addition to a high refractive index. A high‐refractive‐index barrier film has the potential to reduce the refractive‐index mismatch between a device and a protective film, consequently, reducing the energy costs by increasing the light output. In this work, six epoxy and phenoxy resin composite compositions are synthesized separately, each with a different cross‐linker. POL‐TE1/PET and POL‐HD1/PET films show enhanced refractive indexes of 1.726 (at 750 nm) and 1.721 (at 500 nm), allowing only 71.7% and 70.4% permeation, respectively, compared to those of POL/PET, while exhibiting more than 80% transparency and excellent properties. The films are fabricated using a straightforward process, from a solution, at low temperature and under atmospheric conditions, using an applicator and bar coating.