1H NMR Study on the Isomerization of 2,4,6-Triphenyl-4H-Seleno(Thio)Pyrans

It is shown using ¹H NMR spectroscopy that 2,4,6-triphenyl-4H-seleno(thio)pyrans can be isomerized into 2H-isomers by the action of lithium perchlorate or lithium chloride in DMF or only by DMF. The reaction time is found to depend on the Lewis acidity of used salt. It is supposed that isomerization in presence of Lewis acids proceeds as endocyclic 1,3-proton transfer or as a series of two 1,2-hydride shifts.     

Phase Diagrams of Semicrystalline Polymer–Crystalline Substances: Polyolefins–1,2,4,5-Tetrachlorobenzene

The full phase diagrams of low-density polyethylene (LDPE), high-density polyethylene (HDPE), and isotactic polypropylene (i-PP) mixtures with 1,2,4,5-tetrachlorobenzene (TeCB), including the solubility curve of TeCB in a solid polymer, were constructed by an optical method. The diagrams contain a eutectic point that corresponds to the situation when the crystallization of TeCB out of its solution in a polyolefin is accompanied by the crystallization of monomer units of the macromolecules. As a result, the polymer acquires a gel structure with crystallites as crosslinks and amorphous regions saturated with TeCB. It is demonstrated that the eutectic point position on the phase diagram can be used for ranking polymers with respect to their thermodynamic affinity to a solvent. For the studied systems, the affinity to TeCB was decreased in the order i-PP, HDPE, and LDPE. Direct experimental evidence was obtained that TeCB crystals can be dissolved in a solid polymer via a vapor phase mechanism, which leads to the polymer amorphization.     

Boronate Ligands in Materials: Determining Their Local Environment by Using a Combination of IR/Solid‐State NMR Spectroscopies and DFT Calculations

Boronic acids (R‐B(OH)₂) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R‐B(OH)₃^?) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C₄H₉‐B(OH)₃]₂, which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid‐state NMR spectroscopy (¹H, ¹³C, ¹¹B and ⁴³Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave—GIPAW—method). These data allow relationships between the geometry around the OH groups in boronates and the IR and ¹H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic–inorganic materials containing boronate building blocks.     

Electromagnetic wormholes and virtual magnetic monopoles from metamaterials

We describe new configurations of electromagnetic (EM) material parameters, the electric permittivity epsilon and magnetic permeability micro, which allow one to construct devices that function as invisible tunnels. These allow EM wave propagation between the regions at the two ends of a tunnel, but the tunnels themselves and the regions they enclose are not detectable to lateral EM observations. Such devices act as wormholes with respect to Maxwell's equations and effectively change the topology of space vis-à-vis EM wave propagation. We suggest several applications, including devices behaving as virtual magnetic monopoles, invisible cables, and scopes for MRI-assisted surgery.     

Resonant mode oscillations in modulated waveguiding structures

We put forward the concept of resonant, Rabi-like oscillatons and adiabatic transitions between confined light modes in properly modulated multimode waveguides. The phenomenon is shown to take place in both the linear and the nonlinear regimes. In addition, we find that the mode transitions occur not only in simple geometries, but also in complex confining multimode structures. The phenomenon is analogous to the familiar stimulated state transitions that occur in multilevel quantum systems.     

Light emission from nanocrystalline silicon clusters embedded in silicon dioxide: Role of the suboxide states

Silicon clusters embedded in a silicon dioxide matrix were prepared by ultrasound-assisted implantation resulting in a modified concentration of suboxide states as revealed by high-resolution photoelectron spectroscopy. It is suggested that ultrasound treatment results in formation of different interface structure between silicon cluster and silicon dioxide matrix which is characterized by a distinctly reduced concentration of the suboxide states. It is observed that photoluminescence properties are strongly correlated with the concentration of the suboxide states thereby providing an evidence that besides a quantum confinement effect a closer look at the chemical composition of the nc-Si/SiO₂ system is important.     

Higher order numerical differentiation on the Infinity Computer

There exist many applications where it is necessary to approximate numerically derivatives of a function which is given by a computer procedure. In particular, all the fields of optimization have a special interest in such a kind of information. In this paper, a new way to do this is presented for a new kind of a computer—the Infinity Computer—able to work numerically with finite, infinite, and infinitesimal numbers. It is proved that the Infinity Computer is able to calculate values of derivatives of a higher order for a wide class of functions represented by computer procedures. It is shown that the ability to compute derivatives of arbitrary order automatically and accurate to working precision is an intrinsic property of the Infinity Computer related to its way of functioning. Numerical examples illustrating the new concepts and numerical tools are given.     

Transformation of perfluorinated benzocycloalkenes and alkylbenzenes to their carbonyl derivatives under the action of CF3COOH/SbF5

Perfluorinated benzocycloalkenes (benzocyclobutene, indan, tetralin), alkylbenzocycloalkenes and alkylbenzenes react with CF₃COOH/SbF₅ at 20-50 °C giving the corresponding carbonyl derivatives.