(Halomethyl)arsenic compounds : II. Preparation and dynamic NMR spectra of pentakis(chloromethyl)cyclopentaarsine

Hypophosphorous acid reduction of chloromethylarsonic acid produces the novel cyclopolyarsine, pentakis(chloromethyl)cyclopentaarsine (PCCA). PCCA possesses a greater thermal and oxidative stability than other cyclopolyarsines previously studied. The dynamic PMR properties of PCCA are interpreted as a combination of a low-energy limited pseudorotational motion and a higher-energy As-atom inversional process. An alternative to ground-state d-orbital participation in the interpretation of the electronic spectra is offered.     

Resampling student'st-type statistics

The present paper establishes conditional and unconditional central limit theorems for various resampling procedures for thet-statistic. The results work under fairly general conditions and the underlying random variables need not to be independent. Specific examples are then them(n) (double) bootstrap out ofk(n) observations, the Bayesian bootstrap and two-samplet-type permutation statistics. In case whenm(n)/k(n) is bounded away from zero and infinity necessary and sufficient conditions for the conditional central limit law of the bootstrapt-statistics are established. For high resampling intensity whenm(n)/k(n) tends to infinity the following general result is obtained. Without further other assumptions the bootstrap makes the resampledt-statistic automatically normal. The results are based on a general conditional limit theorem for weighted resampling statistics which is of own interest.     

Qualitative theory of stochastic systems and its applications in physics

The aim of this note is just to sketch some of the problems and results of the qualitative theory of Stochastic Dynamical Systems (SDS) relevant to physics and to give reference to papers where details can be found. General references are Arnold [6] and Arnold and Kleinmann [7].     

Minimal spaser threshold within electrodynamic framework: Shape,size and modes

It is known (yet often ignored) from quantum mechanical or energetic considerations, that the threshold gain of the quasi‐static spaser depends only on the dielectric functions of the metal and the gain material. Here, we derive this result from the purely classical electromagnetic scattering framework. This is of great importance, because electrodynamic modelling is far simpler than quantum mechanical one. The influence of the material dispersion and spaser geometry are clearly separated; the latter influences the threshold gain only indirectly, defining the resonant wavelength. We show that the threshold gain has a minimum as a function of wavelength. A variation of nanoparticle shape, composition, or spasing mode may shift the plasmonic resonance to this optimal wavelength, but it cannot overcome the material‐imposed minimal gain. Furthermore, retardation is included straightforwardly into our framework; and the global spectral gain minimum persists beyond the quasi‐static limit. We illustrate this with two examples of widely used geometries: Silver spheroids and spherical shells embedded in and filled with gain materials.     

Structural modifications of polymers under the impact of fast neutrons

Fast neutron irradiations were performed at room temperature on a series of 13 polymer matrixes having great practical and academic interest. Polymers were irradiated with very low doses of 14 MeV neutrons deposited at reduced dose rate. The modifications of chemical structure of the polymeric matrixes resulting from irradiation were analyzed at the molecular scale by infrared and UV-visible spectroscopy. Particular attention was given to the oxidation occurring in irradiated matrixes during storage in the absence of light at room temperature. In addition the effects of irradiation on the chain arrangements in the polymers were analyzed by Differential Scanning Calorimetry.The most significant result obtained in this preliminary work was evidence that neutron irradiation with very low doses in the range ≈130-320 cGy could provoke structural changes. Indeed, depending on the matrixes, the formation of oxidation products along the macromolecular chains or the evolution of the polymer architecture, evidenced by changes of the T_g or of the crystallinity, was observed. The perspectives of this preliminary work are discussed.     

Grain boundaries as barrier for oxygen transport in perovskite-type membranes

Perovskite-type membranes of (Ba_0.5Sr_0.5)(Co_0.8Fe_0.2)O_3−δ (BSCF) and (Ba_0.5Sr_0.5)(Fe_0.8Zn_0.2)O_3−δ (BSFZ) were successfully prepared via liquid-phase sintering using BN as sintering aid. The obtained membranes were examined via powder X-ray diffraction pattern (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and oxygen permeation experiments. It has emerged that the use of BN as sintering aid lowers sintering temperatures in order to obtain dense membranes with relative densities in the range of 93–96% as proven by the Archimedes method. It was further shown that the perovskite structure could be maintained after sintering with BN. Additionally, BN was completely removed from the sintered membranes. Investigation of the microstructure revealed that the average grain size of the membranes was influenced by the amount of BN added prior the sintering process. It was found that large amounts of BN effectively lower the average grain size. Oxygen permeation experiments have shown that the lower the average grain size the lower the oxygen permeation performance, particularly in the case of BSCF. Transmission electron microscopy revealed that no evidence for an amorphous layer or any other interfacial phase in the grain boundary is present.     

Thermodynamic investigation of the adsorption of amides on graphite from their liquids and binary mixtures

We report a thermodynamic investigation of the adsorption of saturated and unsaturated (cis- and trans-) alkyl amides onto the surface of graphite from their pure liquids and from binary mixtures. We identify the formation of solid monolayers of the amides at temperatures when the bulk materials are liquid. The extent of this presolidification is much more extensive than other related materials, indicating that these amide layers are significantly more stable. The monolayer stability is found to be greatest for saturated amides. In addition, the stability of unsaturated amides is extremely sensitive to the location of the double bonds in the alkyl chain of the molecules, and trans isomers are found to be more stable than cis. We also address the preferential adsorption and mixing behavior of amide mixtures and amides mixed with other species coadsorbed onto graphite from binary solution. The results indicate that the amide molecules appear to be adsorbed with their principal axis parallel to the graphite surface and that amides are found to be strongly preferentially adsorbed with respect to alkanes. Interestingly the amides appear to mix rather better than might have been expected. There is also evidence of a number of other transitions in the adsorbates.     

The sol–gel synthesis of perovskites by an EDTA/citrate complexing method involves nanoscale solid state reactions

Nowadays, sol–gel procedures are well established in the synthesis of complex oxides as they allow to obtain phase pure products and to control precisely their stoichiometry. This quality makes them a tool of choice for the preparation of perovskite-type oxides. To optimize the functional properties of these materials, it is essential to set accurately their possible complex stoichiometries. However, details of the formation of the perovskite crystal remain obscure. Different stages of an ethylene-diamine-tetraacetic acid (EDTA)/citrate-gel based synthesis process for mixed conducting (Ba_0.5Sr_0.5)(Fe_0.8Zn_0.2)O_3−δ of cubic perovskite structure are elucidated. The combination of analytical transmission electron microscopy with X-ray diffraction reveals that the perovskite-type oxide is formed already at moderate temperatures at around 700 °C via nanoscale solid state reactions between finely-dispersed crystalline intermediates identified as a spinel and a carbonate. The reaction scheme, however, is intricate and includes stuffed tridymite structures as transient phases. The ultrafine intermixing of extremely small reactants makes EDTA/citrate-gel based procedures superior to classical solid state routes with respect to applications that demand phase purity and stoichiometry control.