Electrostatics and the electro-optic behaviour of chiral smectics C: 'block' polarization screening of applied voltage and 'V-shaped' switching

We present a new model for the physics of thresholdless switching in chiral smectics. In the limit of high polarization, the electro-optics of chiral smectic C liquid crystals are dominated by two distinct electrostatic effects. Complete (surface to surface) 'stiffening' of the polarization field by its charge self-interaction causes the polarization to orient as a uniform block. Complete screening of applied electric field by polarization charge leads to voltage-induced orientation where the electric field in the liquid crystal is exactly zero, These effects, both operative during the 'V-shaped' portion of thresholdless transmission vs. voltage curves, combine to produce 'V-shaped' switching.     

A Sustainable Freeze‐Drying Route to Porous Polysaccharides with Tailored Hierarchical Meso‐ and Macroporosity

Bio‐derived polysaccharide aerogels are of interest for a broad range of applications. To date, these aerogels have been obtained through the time‐ and solvent‐intensive procedure of hydrogel fomation, solvent exchange, and scCO2 drying, which offers little control over meso/macropore distribution. A simpler and more versatile route is developed, using freeze drying to produce highly mesoporous polysaccharide aerogels with various degrees of macroporosity. The hierarchical pore distribution is controlled by addition of different quantities of t‐butanol (TBA) to hydrogels before drying. Through a systematic study an interesting relationship between the mesoporosity and t‐butanol/water phase diagram is found, linking mesoporosity maxima with eutectic points for all polysaccharides studied (pectin, starch, and alginic acid). Moreover, direct gelation of polysaccharides in aqueous TBA offers additional time savings and the potential for solvent reuse. This finding is a doorway to more accessible polysaccharide aerogels for research and industrial scale production, due to the widespread accessibility of the freeze drying technology and the simplicity of the method.

     

Phenylene-Bridged Perylene Monoimides as Acceptors for Organic Solar Cells: A Study on the Structure–Property Relationship

A series of non-fullerene acceptors based on perylene monoimides coupled in the peri position through phenylene linkers were synthesized via Suzuki-coupling reactions. Various substitution patterns were investigated using density functional theory (DFT) calculations in combination with experimental data to elucidate the geometry and their optical and electrochemical properties. Further investigations of the bulk properties with grazing incidence wide angle X-ray scattering (GIWAXS) gave insight into the stacking behavior of the acceptor thin films. Electrochemical and morphological properties correlate with the photovoltaic performance of devices with the polymeric donor PBDB-T and a maximum efficiency of 3.17 % was reached. The study gives detailed information about structure–property relationships of perylene-linker-perylene compounds.     

Accelerating dynamical-fermion computations using the rational hybrid Monte Carlo algorithm with multiple pseudofermion fields

There has been much recent progress in the understanding and reduction of the computational cost of the hybrid Monte Carlo algorithm for lattice QCD as the quark mass parameter is reduced. In this letter we present a new solution to this problem, where we represent the fermionic determinant using n pseudofermion fields, each with an nth root kernel. We implement this within the framework of the rational hybrid Monte Carlo algorithm. We compare this algorithm with other recent methods in this area and find it is competitive with them.     

A computational investigation of 17O quadrupolar coupling parameters and structure in alpha-quartz phase GeO2

Ab initio band-structure calculations based on density functional theory have been completed for alpha-quartz phase GeO2 to obtain electric-field gradients (efg) for oxygen atoms, including those for GeO2 at elevated pressure and temperature. To interpret the resulting efg values and examine correlations between structure and 17O quadrupolar coupling parameters, additional ab initio self-consistent Hartree-Fock molecular orbital calculations were completed. The quadrupolar coupling constant was found to have a strong dependence on Ge-O distance and angleGe-O-Ge, with the quadrupolar asymmetry parameter being primarily dependent on angleGe-O-Ge. Analytical expressions describing these dependencies consistent with earlier investigations of analogous silicate compounds are also reported.     

Scalable bottom‐up assembly of suspended carbon nanotube and graphene devices by dielectrophoresis

Bottom‐up assembly by dielectrophoresis (DEP) has emerged in recent years as a viable alternative to conventional top–down fabrication of electronic devices from nanomaterials, particularly carbon nanotubes and graphene. Here, we demonstrate how this technique can be extended to fabricate devices containing carbon nanotubes and graphene suspended between two electrodes over a back‐gate electrode. The suspended device geometry is critical for the development of nano‐electromechanical devices and to extract maximum performance out of electronic and optoelectronic devices. This technique allows for parallel assembly of devices over large scale. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Aqueous Diels–Alder reactions for thermochemical storage and heat transfer fluids identified using density functional theory

Thermal storage and transfer fluids have important applications in industrial, transportation, and domestic settings. Current thermal fluids have relatively low specific heats, often significantly below that of water. However, by introducing a thermochemical reaction to a base fluid, it is possible to enhance the fluid's thermal properties. In this work, density functional theory (DFT) is used to screen Diels–Alder reactions for use in aqueous thermal fluids. From an initial set of 52 reactions, four are identified with moderate aqueous solubility and predicted turning temperature near the liquid region of water. These reactions are selectively modified through 60 total functional group substitutions to produce novel reactions with improved solubility and thermal properties. Among the reactions generated by functional group substitution, seven have promising predicted thermal properties, significantly improving specific heat (by as much as 30.5%) and energy storage density (by as much as 4.9%) compared to pure water.     

Total Syntheses of 11-Acetoxy-4-deoxyasbestinin D, 4-Deoxyasbestinin C,Asbestinin-10, -20, -21 and -23

Six members of the asbestinin family of marine diterpene natural products have been synthesized in an efficient and stereoselective manner from a single oxa-bridged intermediate. Five of these natural products have not been synthesized previously and the structures of four of them have been confirmed as those proposed originally or following revisions to the original structures. The fifth natural product—asbestinin-21—has been shown to be a diastereomer of the compound that had been proposed previously.