Thermodynamic analysis of the chemical exchange of beta-phosphorylated cyclic nitroxides by using two-dimensional (temperature versus magnetic field) simulation of ESR spectra: the impact of labile solvent-solute interactions on molecular dynamics

A complete thermodynamic characterization of the chair-to-chair interconversion in beta-diphosphorylated piperidine-N-oxyl radicals was achieved by means of the analysis of temperature-dependent ESR spectra. A new two-dimensional simulation method was developed with the coordinates temperature and magnetic field, in which the entire set of spectra was simulated simultaneously by adjusting the coefficients in the power expansion, giving the temperature-dependent ESR parameters and the thermodynamic and kinetic parameters determining the site populations and exchange rates, respectively. The new method promotes elimination of the ambiguities inherent in the spectroscopic determination of thermodynamic parameters. Labile solvent-solute interactions can strongly influence the chemical exchange, producing a complex network of symmetric and asymmetric interconversions. The solvent dependence of magnetic relaxation was also analyzed.     

Acoustic metafluids made from three acoustic fluids

Significant reduction in target strength and radiation signature can be achieved by surrounding an object with multiple concentric layers comprised of three acoustic fluids. The idea is to make a finely layered shell with the thickness of each layer defined by a unique transformation rule. The shell has the effect of steering incident acoustic energy around the structure, and conversely, reducing the radiation strength. The overall effectiveness and the precise form of the layering depends upon the densities and compressibilities of the three fluids. Nearly optimal results are obtained if one fluid has density equal to the background fluid, while the other two densities are much greater and much less than the background values. Optimal choices for the compressibilities are also found. Simulations in 2D and 3D illustrate effectiveness of the three fluid shell. The limited range of acoustic metafluids that are possible using only two fluid constituents is also discussed.     

Highly efficient thermal cyclization reactions of alkylidene esters in continuous flow to give aromatic/heteroaromatic derivatives

Intramolecular thermal cyclization and benzannulation reactions of the Gould–Jacobs and Conrad–Limpach types were performed in a designed continuous flow reactor system at temperatures in the range of 300–360 °C and under high pressure conditions (100–160 bar) with very short residence times (0.45–4.5 min) in tetrahydrofuran as a low-boiling point solvent. Substituted heteroaromatic compounds including pyridopyrimidinones and hydroxyquinolines were synthesized in moderate to high yields. Application of the reaction conditions also allows the synthesis of naphthol and biphenyl derivatives. The procedure involves an easy work-up and the non-batchwise preparative synthesis method is suitable for automation.     

Surface morphology of as-deposited and illuminated As–Se chalcogenide thin films

The role of the composition and of the related changes of the structure in the formation of the surface of amorphous As_xSe_1−x (0 < x < 0.5) layers before and after light treatment was investigated by direct measurements of the surface roughness at nanometer-scale and surface deformations at micrometer-scale under influence of illumination. It was established that the surface roughness of the films, deposited by vacuum thermal evaporation, decreased with increasing As content, especially in compositions 0.1  x  0.3, where the maximum light stimulated surface deformations (localized expansion) occurs. Both relate to the rigidity percolation range and the maximum photoplastic effects, which are not directly connected to the known photodarkening effect, since it is minimal for these compositions.     

Nonlinear screening in two-dimensional electron gases

We have performed self-consistent calculations of the nonlinear screening of a point charge Z in a two-dimensional electron gas using a density functional theory method. We find that the screened potential for a Z=1 charge supports a bound state even in the high-density limit where one might expect perturbation theory to apply. To explain this behavior, we prove a theorem to show that the results of linear response theory are in fact correct even though bound states exist.     

Fe-induced magnetic transition in YBa2(Cu1−x 57Fe x )3O6 by NQR and Mössbauer spectroscopy

Nuclear quadrupole resonance spectroscopy (around 30 MHz) on the chain site Cu(1) nuclei in oxygen deficient YBa₂(Cu_1?x Fe _x )₃O₆ doped with different amounts of⁵⁷Fe (x≤0.01) reveal an onset of magnetic order at low temperatures represented by a symmetrical doublet contribution to the nuclear quadrupole resonance (NQR) spectrum. The onset temperatureT _N2 depends on the concentration of Fe reaching 130 K forx=0.01. The splitting forx=0.01 at 100 K corresponds to a net internal field of 0.09 T with a distribution of ≈0.08 T representing about 70 percent of the Cu(1) nuclei.⁵⁷Fe and⁵⁷Co Mössbauer spectroscopy at 4.2 K with and without an external magnetic field of 5 T revealed that belowx=0.00015 Fe spins are decoupled from the Cu(2) moments in the antiferromagnetic state. Results are interpreted in terms of the magnetic model structure suggested by Kadowaki et al. [1].     

In vivo measurements with a potassium ion-selective microelectrode based on a new bis(crown ether)

Potassium ion-selective microelectrodes with a tip diameter of 10 μm are described. The ionophore used is 2,2′-bis[3,4-(15-crown-5)-2-nitrophenylcarbamoxymethyl] tetradecane in a conventional mixture with sodium tetraphenylborate, an ether and PVC. The electrode provides Nernstian response over the range 10^?5?10^?1 M potassium activity. Its selectivity is shown to be similar to that of a valinomycin-based microelectrode. After the electrode has aged for 24 h, the 95% response time at the 10^?3 M potassium ion level is 2.0 ± 0.5 s. The applicability of the bis(crown ether) electrode for measurements in vivo is proved by monitoring the changes in potassium activity in different areas of the brain of anaesthetized rats after administration of veratrine.     

Synthesis,Mössbauer,and IP spectroscopic studies and thermal behavior of diorganotin(IV) complexes with carbohydrate ligands

A series of diethyltin(IV) complexes with carbohydrate ligands (aldoses, polyalcohols, sugar acids, sugar amines, and di- and trisaccharides] was prepared. The compositions of the complexes were determined by standard analytical methods. The results showed that complexes formed containing the diethyltin moiety and the carbohydrate ligand in 11 ratio. The IR spectra were consistent with the presence of tin—carbohydrate oxygen vibrations in the compounds. The comparison of experimental quadrupole splitting values with those calculated on the basis of the partial quadrupole splitting (PQS) concept revealed the compounds to be of three types: complexes in with the central tin(IV) atoms are present in purely trigonal bipyramidal surroundings, ones with the tin(IV) atoms present in purely octahedral surroundings, or ones with both octahedral and trigonal bipyramidal arrangements in approximately 11 ratio. The thermal decompositions showed that some of the complexes decompose via the reduction of tin(IV) to SnO as the final tin-containing product, some of them decompose without reduction, to give SnO₂, and some decompose to give indefinite final tin-containing products.     

Large t elastic proton-proton scattering at √s = 53 GeV

New experimental results are presented on proton-proton elastic scattering in the range of momentum transfer 0.8GeV² < ?t < 9 GeV² at a centre-of-mass energy of √s = 53 GeV. The data are obtained sing the Split-Field- Magnet Detector at the CERN Intersecting Storage Rings. The cross section has well-known minimum at ?t = (1.34±0.02) GeV² but no further minimum or change of slope is observed between 2 and 6.5 GeV².