Aggregation of clay platelets in nematic liquid crystal, 5CB: microstructure,electrical conductivity and rheological investigations

The microstructure, electrical conductivity and rheological properties of a nematic liquid crystal (5CB) doped at concentrations up to 4.5 wt% of montmorillonite (MMT) or organomontmorillonite (OMMT) clay nanoplatelets, were investigated at temperatures between 293 and 310 K. Microscopy and electrical conductivity assessment revealed noticeable differences in aggregation in MMT and OMMT suspensions, MMT nanoplatelets showing a strong tendency to aggregation. The incubation of 5CB in the presence of MMT initially produced loose aggregation, followed by the formation of compact aggregates. The latter had practically no influence on the surrounding inter-aggregate regions. In the case of OMMT, a greater degree of integration of the nanoplatelets was observed within the liquid crystal structure of 5CB, resulting in a noticeable effect on electrical conductivity and activation energy of the composite material. Thixotropy was observed in suspensions of 5CB composites formed with either MMT or OMMT. A composite of 5CB with OMMT also exhibited anomalous viscous thinning at shear rates below 100 s^?1. A structural model is suggested to explain this behaviour.     

Amorphous Calcium Phosphates: Solvent-Controlled Growth and Stabilization through the Epoxide Route

Calcium phosphates stand among the most promising nanobiomaterials in key biomedical applications, such as bone repairment, signalling or drug/gene delivery. Their intrinsic properties as crystalline structure, composition, particle shape and size define their successful use. Among these compounds, metastable amorphous calcium phosphate (ACP) is currently gaining particular attention due to its inherently high reactivity in solution, which is crucial in bone development mechanisms. However, the preparation of this highly desired (bio)material with control over its shape, size and phase purity remains as a synthetic challenge. In this work, the epoxide route was adapted for the synthesis of pure and stable ACP colloids. By using biocompatible solvents, such as ethylene glycol and/or glycerine, it was possible to avoid the natural tendency of ACP to maturate into more stable and crystalline apatites. Moreover, this procedure offers size control, ranging from small nanoparticles (60 nm) to micrometric spheroids (>500 nm). The eventual fractalization of the internal mesostructured can be tuned, by simply adjusting the composition of the ethylene glycol:glycerine solvent mixture. These findings introduce the use of green solvents as a new tool to control crystallinity and/or particle size in the synthesis of nanomaterials, avoiding the use of capping agents and preserving the natural chemical reactivity of the pristine surface.     

Azimuthal orientational correlations due to excluded volume epitaxy in growing anisotropic grains

The microstructure of anisotropically shaped grains can strongly influence a range of material properties, including transport, mechanical and electro-optical. A grain-structure-related phenomenon, known as excluded volume epitaxy (EVE), is reported in this study. EVE is a local, inter-grain orientational correlations effect, which results from a combination of continuous nucleation of anisotropic grains and impingement of growing grains. Due to EVE, anisotropically shaped grains have a tendency to be similarly aligned in a local neighbourhood, despite the absence of any forced global orientation in the sample. The effect has been repeatedly observed by the authors in block copolymers, as illustrated by a representative TEM image. Optical microscopy of anisotropically shaped non-polymeric crystals revealed the generality of this effect. The simulation study revealed a tendency for azimuthal, inter-grain orientational correlation and re-confirmed the experimental observation of EVE.     

Solvation Dynamics of a Radical Ion Pair in Micro‐Heterogeneous Binary Solvents: A Semi‐Quantitative Study Utilizing MARY Line‐Broadening Experiments

This work aims at elucidating the mechanism of solvation of a radical ion pair (RIP) in a micro‐heterogeneous binary solvent mixture using magnetically affected reaction yield (MARY) spectroscopy. For the exciplex‐forming 9,10‐dimethylanthracene/N,N‐dimethylaniline system a comparative, composition‐dependent MARY line‐broadening study is undertaken in a heterogeneous (toluene/dimethylsulfoxide) and a quasi‐homogenous (propyl acetate/butyronitrile) solvent mixture. The half‐saturation field extrapolated to zero‐quencher concentration, B_1/2, and the self‐exchange rate constants are analyzed in the light of solvent dynamical properties of the mixtures and a dielectric continuum solvation model. The dependence of B_1/2 on the solvent composition is explained by cluster formation giving rise to shortened RIP lifetimes. The results are in qualitative agreement with the continuum solvation model suggesting that it could serve as a theoretical basis for quantitative modeling.     

Micro-/Mesoporous conjugated polymer based on star-shaped triazine-functional triphenylamine framework as the performance-improved cathode of Li-organic battery

A novel organic conjugated polymer based on star-shaped triazine-functional triphenylamine framework poly[1,3,5-tris(4-diphenylamino-phenyl)triazine] (PTDAPTz) is designed and synthesized successfully by FeCl₃-catalysted chemical oxidative polymerization. The polymer PTDAPTz powder exhibits a compactly packed pleated skirt shape-like morphology with a high surface area (~930 m² g⁻¹) and a bimodal pore size distribution ranging from micropores (~0.55 nm) to small diameter mesopores (~2–6 nm). As explored as the cathode material, the obtained PTDAPTz presents the double charge–discharge process characteristics of both the free radical redox of triphenylamine unit and the bipolar redox of triazine unit in the polymer and a well-defined multistage charge/discharge voltage plateau (~3.8 V for p-doped and ~2.0 V for n-doped) during the charge–discharge process. Also, the PTDAPTz demonstrates an improved capacity (stabilized at 123 mA h g⁻¹ until 50th cycle) and the enhanced rate performance compared to polytriphenylamine (PTPAn). Specially, the discharge curve for the part of triphenylamine unit presents an obviously improved discharge plateau (~3.8 V for PTDAPTz compared to ~3.6 V for PTPAn) due to the electron-withdrawing effect of the triazine unit to triphenylamine. The elaborate structural design and created micro-/mesoporous morphology with the double charge–discharge process make PTDAPTz a potential candidate as the performance-improved cathode of Li-organic battery. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2574–2583     

Crystallographic and microstructural aspects of the superconductor YBa2Cu3O7-y —an overview

Crystal structures and structural inhomogeneities observed in YBa₂Cu₃O_7-y are reviewed. It is brought out that a proper understanding of the nature of the structural inhomogeneities is essential for exploiting the technological potential of this material. The need for an adequate characterization of specimens used for experiments is emphasized. Practical implications of the ferroelastic nature of the material are discussed.     

A trading mechanism contingent on several indices

We introduce a trading mechanism where the execution of an order on a security can be made contingent on the relation between the clearing price of the security and the clearing price of one or several indices. A mechanism similar to ours, but limited to only one index, was implemented on the Tel Aviv Stock Exchange. We argue that it is in some cases crucial to make the execution of an order contingent on several indices. Our mechanism consists of a particular implementation of a double-sided multi-unit combinatorial auction with substitutes (or DMCS auction), which we introduced in an earlier article.     

Supramolecular heterogeneity in β-turn forming synthetic tripeptides nucleated by isomers of fluorinated phenylalanine and aib as corner residues

The influences of fluorines in chemistry have emerged as a breakthrough in various arenas of bio-organic and medicinal chemistry. But its incorporation in β-turn design and its implications for supramolecular chemistry remains in a rudimentary stage. Inspired by the diversity displayed by the isomers of mono-fluorinated phenylalanine in biological sciences, here our effort is to modulate the solid state conformational analysis of three terminally protected synthetic tripeptides Boc-(Y)-F-Phe-Aib-Xaa-OMe, where (Y is (2)-F-Phe, Xaa; Leu in peptide I, (3)-F-Phe, Xaa; Leu in peptide II and (4)-F-Phe, Xaa; Ile in peptide III). Interestingly, all the three peptides display a conformational preference for β-turns, stabilized by 4→1 intramolecular hydrogen bonding. Our investigation further demonstrates that mere interchange of positions of fluorines in mono-fluorinated phenylalanine in peptides I–III introduces significant diversity in supramolecular chemistry. X-ray crystallography sheds some light at atomic resolution. Furthermore, this supramolecular heterogeneous behavior is evident from the morphologies obtained from the materials of all the three peptides grown from acetone to petroleum ether solution, studied by field emission scanning electron microscopy. Thus, these monofluorinated peptides I–III may serve as prominent candidates in understanding the structure and function of misfolded disease causing peptides like prion and Alzheimer's amyloid.     

Arraying Cell Cultures Using PEG‐DMA Micromolding in Standard Culture Dishes

A robust and effortless procedure is presented, which allows for the microstructuring of standard cell culture dishes. Cell adhesion and proliferation are controlled by three‐dimensional poly(ethylene glycol)‐dimethacrylate (PEG‐DMA) microstructures. The spacing between microwells can be extended to millimeter size in order to enable the combination with robotic workstations. Cell arrays of microcolonies can be studied under boundary‐free growth conditions by lift‐off of the PEG‐DMA layer in which the growth rate is accessible via the evolution of patch areas. Alternatively, PEG‐DMA stencils can be used as templates for plasma‐induced patterning.