Synthesis of Per- and Poly-Substituted Trehalose Derivatives: Studies of Properties Relevant to Their Use as Excipients for Controlled Drug Release

Per- and poly-substituted oligosaccharide derivatives, with trehalose cores, have been prepared and assessed for their potential for use as excipients in controlled-release formulations. The synthesized compounds, generally with acyl and amido substituents, included 6,6′-N,N′ -diamido-6,6′ -dideoxy-α,α -trehalose derivatives, 6,6′ -bis(1,2,3,4-tetra-O-acetyl-β -D-glucopyranuronyl)-α, α -trehalose derivatives, 2,2′,3,3′ -tetra-O-acetyl-6,6′ -bis-(1,2,3,4-tetra-O-acetyl-β-D-glucopyranuronyl)-4,4′ -di-O-acyl-α,α-trehalose, 2, 2′, 3, 3′ -tetra-O-acetyl-6-(1,2,3,4-tetra-O-acetyl-β-D-glucopyranuronyl)-4,4′,6′ -tri-O-acyl-α,α-trehalose, and 2,2′,3,3′,4,4′ -hexa-O-acetyl-6,6′ -bis-(1,2,3,4-tetra-O-acetyl-6-O-succinyl-β-D-glucopyranuronyl)-α,α-trehalose. Compounds were characterized by NMR, IR, MS and optical rotations; elemental analyses; or HRMS. The compounds formed amorphous materials either on fast quenching of melts or on spray drying. Properties, used in the initial assessment of the potential as controlled-release excipients, were log₁₀ P and glass transition, T_g, values.     

CO Oxidation Catalytic Effects of Intrinsic Surface Defects in Rhombohedral LaMnO3

There is an ongoing effort to replace rare and expensive noble-element catalysts with more abundant and less expensive transition metal oxides. With this goal in mind, the intrinsic defects of a rhombohedral perovskite-like structure of LaMnO₃ and their implications on CO catalytic properties were studied. Surface thermodynamic stability as a function of pressure (P) and temperature (T) were calculated to find the most stable surface under reaction conditions (P=0.2 atm, T=323 K to 673 K). Crystallographic planes (100), (111), (110), and (211) were evaluated and it was found that (110) with MnO₂ termination was the most stable under reaction conditions. Adsorption energies of O₂ and CO on (110) as well as the effect of intrinsic defects such as Mn and O vacancies were also calculated. It was found that O vacancies favor the interaction of CO on the surface, whereas Mn vacancies can favor the formation of carbonate species.     

Topological nature of in‐gap bound states in disordered large‐gap monolayer transition metal dichalcogenides

We propose a physical model based on disordered (a hole punched inside a material) monolayer transition metal dichalcogenides (TMDs) to demonstrate a large‐gap quantum valley Hall insulator. We find an emergence of bound states lying inside the bulk gap of the TMDs. They are strongly affected by spin–valley coupling, rest‐ and kinetic‐mass terms and the hole size. In addition, in the whole range of the hole size, at least two in‐gap bound states with opposite angular momentum, circulating around the edge of the hole, exist.Their topological insulator (TI) feature is analyzed by the Chern number, characterized by spacial distribution of their probabilities and confirmed by energy dispersion curves (energy vs. angular momentum). It not only sheds light on overcoming low‐temperature operating limitation of existing narrow‐gap TIs, but also opens an opportunity to realize valley‐ and spin‐qubits. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Topological transition in coated wire medium

Employing nonlocal homogenization approach, we investigate the properties of a metamaterial consisting of parallel metallic wires with dielectric coating. We demonstrate that manipulation of dielectric contrast between wire dielectric shell and host material at fixed frequency results in dynamic switching of metamaterial dispersion regime from elliptic to the hyperbolic one, i.e. the topological transition takes place. It is proved that such transition can be induced by the variation of the metamaterial temperature. Our findings thus pave a way to the implementation of a tunable ‘elliptic‐hyperbolic’ metamaterial.     

Electric field induced metal–insulator transition in VO2 thin film based on FTO/VO2/FTO structure

A VO₂ thin film has been prepared using a DC magnetron sputtering method and annealing on an F-doped SnO₂ (FTO) conductive glass substrate. The FTO/VO₂/FTO structure was fabricated using photolithography and a chemical etching process. The temperature dependence of the I–V hysteresis loop for the FTO/VO₂/FTO structure has been analyzed. The threshold voltage decreases with increasing temperature, with a value of 9.2 V at 20 °C. The maximum transmission modulation value of the FTO/VO₂/FTO structure is 31.4% under various temperatures and voltages. Optical modulation can be realized in the structure by applying an electric field.     

Generalized excluded volume and the diffusivity and viscosity of supercooled liquids and glasses over the entire fragility spectrum

Transport properties of glass-formers near glass transition reflect the varying degrees of the sensitivity of the solid-like dynamics and structures with respect to temperature, depending on their fragility. Notably, however, most glasses resume Arrehenius transport behavior upon onset of vitrification. To address this phenomenon a theory of the self-diffusion coefficient and viscosity is developed on the basis of a model constructed for the generalized excluded volume of glass-formers described by the generic van der Waals equation of state. The molecular clustering behavior of a glass-former is exploited in terms of an order parameter that measures the concentration of glassy, clustered molecules, which is then related to the excluded volume. The formulas arrived therefrom are shown to excellently account for the self-diffusion coefficient and viscosity of various glass-formers over the entire fragility spectrum studied experimentally: e.g., _GeO2${\mathrm{GeO}}_2$, silica, ethanol, glycerol, diopside, propylene carbonate, o$o$-terphenyl, tris-napthylbenzene, toluene, and so on. The excluded volume effect thus investigated is shown to essentially characterize the fragility of the glass-formers. The resulting theory not only predicts for fragile glass-formers to resume Arrehenius transport behavior upon the onset of the glass transition, but also explains a crossover between strong and fragile glass-formers in their diffusivity and viscosity profiles as vitrification sets in.     

动态加载过程中石英玻璃诱导水的快速结晶相变

在气炮加载试验中利用弹载光源原位测试技术,观测了夹于石英玻璃之间的水在动态压缩过程中的透光特性. 通过其光透射特性研究了水的冲击相变. 实验结果发现液态水在动态冲击压缩过程中, 其压力低于2 GPa 就出现透明性变差的现象,而且水的透明性下降与石英玻璃的存在有关,是一种石英诱导水的结晶相变现象.     

Characterization of Cr‐doped Sb2Te3 films and their application to phase‐change memory

Phase‐change memory (PCM) is regarded as one of the most promising candidates for the next‐generation nonvolatile memory. Its storage medium, phase‐change material, has attracted continuous exploration. Along the traditional GeTe–Sb₂Te₃ tie line, the binary compound Sb₂Te₃ is a high‐speed phase‐change material matrix. However, the low crystallization temperature prevents its practical application in PCM. Here, Cr is doped into Sb₂Te₃, called Cr–Sb₂Te₃ (CST), to improve the thermal stability. We find that, with increase of the Cr concentration, grains are obviously refined. However, all the CST films exhibit a single hexagonal phase as Sb₂Te₃ without phase separation. Also, the Cr helps to inhibit oxidation of Sb atoms. For the selected film CST_10.5, the resistance ratio between amorphous and crystalline states is more than two orders of magnitude; the temperature for 10‐year data retention is 120.8 °C, which indicates better thermal stability than GST and pure Sb₂Te₃. PCM cells based on CST_10.5 present small threshold current/voltage (4 μA/0.67 V). In addition, the cell can be operated by a low SET/RESET voltage pulse (1.1 V/2.4 V) with 50 ns width. Thus, Cr–Sb₂Te₃ with suitable composition is a promising novel phase‐change material used for PCM with high speed and good thermal stability performances. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)