Enantiomerically Pure [2.2]Paracyclophane-4-thiol: A Planar Chiral Sulfur-Based Building Block Readily Available by Resolution with an Amino Acid Chiral Auxiliary

Acyl chloride of N-phthaloyl-(S)-isoleucine is an efficient chiral auxiliary for the resolution of (+/-)-[2.2]paracyclophane-4-thiol. A preparative protocol, based on the conversion into diastereoisomeric thiolesters and separation by two fractional crystallizations and column chromatography, was developed. Deprotection with LiAlH4 allowed isolation of the individual thiol enantiomers in good yield (similar to 40%) and high enantiomeric purity (ee >93%). The absolute configurations were determined by comparison of the optical rotation value of the products with literature data and were confirmed by X-ray crystallography

Low temperature shape relaxation of 2-d islands by edge diffusion

We present a precise microscopic description of the limiting step for low temperature shape relaxation of two dimensional islands in which activated diffusion of particles along the boundary is the only mechanism of transport allowed. In particular, we are able to explain why the system is driven irreversibly towards equilibrium. Based on this description, we present a scheme for calculating the duration of the limiting step at each stage of the relaxation process. Finally, we calculate numerically the total relaxation time as predicted by our results and compare it with simulations of the relaxation process.Comment: 11 pages, 5 figures, to appear in Phys. Rev.

Synthesis of macrocyclic receptors with intrinsic fluorescence featuring quinizarin moieties

An unprecedented class of macrocycles with intrinsic fluorescence consisting of phenolic trimers and quinizarin is developed. Though they are lacking strong hydrogen bonds as observed in calixarenes, the two examples introduced here each adopt a vase-like conformation with all four aromatic units pointing in one direction (syn orientation). This “cone” conformation has been confirmed by NMR spectroscopy, molecular modeling, and X-ray crystallography. The laminar, electron-rich fluorophore as part of the macrocycle allows additional contacts to enclosed guest molecules

Hybrid nanoparticles based on sulfides, oxides, and carbides

The methods for synthesis of hybrid nanoparticles based on sulfides, oxides, and carbides of heavy and transition metals were considered. The problem of the influence of the method of synthesis of the hybrid nanoparticles on their atomic structure, morphology of the nanomaterials, and functional properties was analyzed. The areas of practical use of the hybrid nanoparticles were proposed. © 2013 Springer Science+Business Media New York

Elastic Moduli of Nanoglasses and Melt-Spun Metallic Glasses by Ultrasonic Time-of-Flight Measurements

The elastic moduli of the metallic nanoglasses Fe$_{86}$Sc$_{14}$, Fe$_{90}$Sc$_{10}$, Cu$_{58}$Zr$_{42}$, and Cu$_{60}$Zr$_{40}$ were determined by measuring their longitudinal and shear wave velocities together with their densities. The data were compared to the elastic moduli of the conventional meltspun metallic glass counterparts of the same chemical composition. The elastic moduli for the nanoglasses were significantly smaller than those of the metallic glass counterparts. Finally, a comparison was made between the data for nanoglasses and metallic glasses from the literature

Elastic Moduli of Nanoglasses and Melt-Spun Metallic Glasses by Ultrasonic Time-of-Flight Measurements

The elastic moduli of the metallic nanoglasses Fe86Sc14, Fe90Sc10, Cu58Zr42, and Cu60Zr40 were determined by measuring their longitudinal and shear wave velocities together with their densities. The data were compared to the elastic moduli of the conventional melt-spun metallic glass counterparts of the same chemical composition. The elastic moduli for the nanoglasses were significantly smaller than those of the metallic glass counterparts. Finally, a comparison was made between the data for nanoglasses and metallic glasses from the literature

Comparison of the Structure of Grain Boundaries in Silicon and Diamond by Molecular-Dynamics Simulations

Molecular-dynamics simulations were used to synthesize nanocrystalline silicon with a grain size of up to 75 {angstrom} by crystallization of randomly misoriented crystalline seeds from the melt. The structures of the highly-constrained interfaces in the nanocrystal were found to be essentially indistinguishable from those of high-energy bicrystalline grain boundaries (GBs) and similar to the structure of amorphous silicon. Despite disorder, these GBs exhibit predominantly four-coordinated (sp{sup 3}-like) atoms and therefore have very few dangling bonds. By contrast, the majority of the atoms in high-energy bicrystalline GBs in diamond are three-coordinated (sp{sup 2}-like). Despite the large fraction of three-coordinated GB carbon atoms, they are rather poorly connected amongst themselves, thus likely preventing any type of graphite-like electrical conduction through the GBs

Admixed pellets for fast and efficient delivery of plasma enhancement gases: Investigations at AUG exploring the option for EU-DEMO

Gas and pellet injection are envisaged for particle fuelling in EU-DEMO. The gas system will provide edge and divertor fuelling and any further gas species required for operation. Pellets, mm-sized bodies formed from solid hydrogen fuel, are designed for efficient and fast core fuelling. However, they can also be employed for a more efficient delivery of plasma enhancement gases, by admixing them with the fuelling pellets. To check this option for EU-DEMO, explorative investigations have been performed at ASDEX Upgrade (AUG). The AUG system produces ice in a batch process sufficient for about 100 pellets, initially designed for operation with pure H$_2$ or D$_2$. On a trial basis, pellet formation was tested using an H$_2$/D$_2$ mixture and admixtures containing small amounts (up to 2 mol%) of N$_2$, Ar, Kr or Xe in the D$_2$ host. A homogeneous and reproducible ice composition was found for the H$_2$/D$_2$ = 1:1 case. For all the admixed gases, a depletion of the admixture in the ice with increasing atomic number is observed. Nevertheless, the fast and efficient delivery of admixed pellets was clearly demonstrated in dedicated plasma experiments at AUG. Detailed investigations showed that the Ar supplied via admixed pellets has a higher radiation efficiency and a faster radiation rise than an Ar/D$_2$ gas puff. Furthermore, Ar density measurements in a discharge with admixed pellet injection show reasonable agreement with findings of a fading admixed species’ concentration along the ice rod and assumptions on the pellet ablation location in the plasma. Investigations performed at the Oak Ridge National Laboratory with a large batch extruder using up to 2 mol% Ne in D$_2$ confirmed that production of much larger ice quantities can be achieved. These initial explorative investigations clearly reveal the great potential of admixed pellets, although they also demonstrate that further technology efforts are required before their benefits can be utilized

Comparison of the structure of grain boundaries in silicon and diamond by molecular-dynamics simulations

Molecular-dynamics simulations were used to synthesize nanocrystalline silicon with a grain size of up to 75 {angstrom} by crystallization of randomly misoriented crystalline seeds from the melt. The structures of the highly-constrained interfaces in the nanocrystal were found to be essentially indistinguishable from those of high-energy bicrystalline grain boundaries (GBs) and similar to the structure of amorphous silicon. Despite disorder, these GBs exhibit predominantly four-coordinated (sp{sup 3}-like) atoms and therefore have very few dangling bonds. By contrast, the majority of the atoms in high-energy bicrystalline GBs in diamond are three-coordinated (sp{sup 2}-like). Despite the large fraction of three-coordinated GB carbon atoms, they are rather poorly connected amongst themselves, thus likely preventing any type of graphite-like electrical conduction through the GBs