The influence of the liquid crystalline core geometry on the mesogenicity of novel chiral 2-(4-substituted-phenoxy)propanonitriles

The synthesis and characterization of seven novel (R)-2-(4-substituted-phenoxy)propanonitriles are described. The propanonitriles were prepared to evaluate their potential use as thermochromics and ferroelectric dopants, as well as to determine their twist sense properties. The materials exhibit smectic and chiral nematic phases of high thermal stability; the mesogenic behaviour of the nitriles is directly related to the type of two-ring core unit employed. The effects of the different molecular geometries and polarizabilities of the liquid crystalline cores on mesophase stability are discussed, particularly in relation to other members of this series. The chiral nematic phase of the propanonitriles is assigned as having a left-handed twist sense from contact preparation studies, and this is in agreement with rules relating absolute configuration and molecular structure to helical twist sense.     

Metal–Nitrosyl complexes as a source of new vasodilators: Strategies derived from systematic chemistry and nitrosyl ligand reactivity

A series of nitrosyl complexes of empirical formula K_n[M(CN)₅NO], where M = V, Cr, Mn and Co and n = 3, or M = Mo and n = 4, have been prepared which are notional analogues of the widely used vasodilator sodium nitroprusside. Their reactivity towards common nucleophiles (OH^?, NH₂R, NHR₂, HS^? and RS^?), acid and photolysis has been investigated to elucidate the desired properties required of new metal nitrosyls which may have some potential as new non-cyanide-based vasodilators.     

Electrochemical characterization of composite membranes based on crown-ethers intercalated into montmorillonite

Oxyethylene macrocyclic compounds (crown-ethers) act as ligands of intracrystalline cations of certain layered silicates as montmorillonites. Stable intercalation materials are formed which are used to prepare organic-inorganic membranes by encapsulating these intercalation compounds with a poly-butadiene thin coating. Electrochemical Impedance Spectroscopy (EIS) is used to study the resulting composite membranes in contact with aqueous electrolytes. From the impedance plots, the ionic resistance of the membranes is obtained. The thickness of the polybutadiene coating is an important factor determining the ability of ions to pass across the membrane. Marked differences in the ionic resistance are observed as a function of the nature of the interlayer macrocyclic compound. For non-intercalated montmorillonite membranes, the ionic resistance is strongly reduced, whereas for some crown-ether intercalated materials such as 18-crown-6 and dibenzo 24-crown-8, iono-selective membranes are obtained. Concerning the nature of the electrolyte, cations exhibiting greater hydration energies show higher difficulties to pass through the membrane and, consequently, the ionic resistance increases.     

Kinetic model for hydrocarbon-assisted particulate boron combustion

A kinetic model is presented to describe the high temperature (1800 K < T < 3000 K) surface oxidation of particulate boron in a hydrocarbon combustion environment. The model includes a homogeneous gas-phase B/O/H/C oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multi-component gas-phase diffusion, and a heterogeneous surface oxidation mechanism consisting of ‘elementary’ adsorption and desorption reaction steps. Thermochemical and kinetic parameters for the surface reactions are estimated from available experimental data and/or elementary transition state arguments. The kinetic processes are treated using a generalized kinetics code, with embedded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. Model results are presented for the oxidation of a 200 μm boron particle in a JP-4/air mixture at ambient temperatures of 1400 K and 2000 K. These results include temperature and gas-phase species profiles as a function of radial distance and particle burning rates. © 1994 John Wiley & Sons, Inc.     

Large Sample Properties of Mixture Models with Covariates for Competing Risks

We study the large-sample properties of a class of parametric mixture models with covariates for competing risks. The models allow general distributions for the survival times and incorporate the idea of long-term survivors. Asymptotic results are obtained under a commonly assumed independent censoring mechanism and some modest regularity conditions on the survival distributions. The existence, consistency, and asymptotic normality of maximum likelihood estimators for the parameters of the model are rigorously derived under general sufficient conditions. Specific conditions for particular models can be derived from the general conditions for ready check. In addition, a likelihood-ratio statistic is proposed to test various hypotheses of practical interest, and its asymptotic distribution is provided.     

Realization of an OpenMath Server for REDUCE

Various approaches and standards for transferring mathematical objects between different computer programs in multimedia environment in the framework of the OpenMath project are described. The use of these standards might revolutionize the exchange of mathematical information caused by the development of computer algebra tools and telecommunication possibilities. The standards make it possible to create databases and easily save and use mathematical objects obtained in different applications, e.g., to exchange the data obtained in different computer algebra systems and place information on the Internet. Bibliography: 9 titles.     

STATISTICAL ENERGY ANALYSIS OF COUPLED PLATE SYSTEMS WITH LOW MODAL DENSITY AND LOW MODAL OVERLAP

Finite element methods, experimental statistical energy analysis (ESEA) and Monte Carlo methods have been used to determine coupling loss factors for use in statistical energy analysis (SEA). The aim was to use the concept of an ESEA ensemble to facilitate the use of SEA with plate subsystems that have low modal density and low modal overlap. An advantage of the ESEA ensemble approach was that when the matrix inversion failed for a single deterministic analysis, the majority of ensemble members did not encounter problems. Failure of the matrix inversion for a single deterministic analysis may incorrectly lead to the conclusion that SEA is not appropriate. However, when the majority of the ESEA ensemble members have positive coupling loss factors, this provides sufficient motivation to attempt an SEA model. The ensembles were created using the normal distribution to introduce variation into the plate dimensions. For plate systems with low modal density and low modal overlap, it was found that the resulting probability distribution function for the linear coupling loss factor could be considered as lognormal. This allowed statistical confidence limits to be determined for the coupling loss factor. The SEA permutation method was then used to calculate the expected range of the response using these confidence limits in the SEA matrix solution. For plate systems with low modal density and low modal overlap, relatively small variation/uncertainty in the physical properties caused large differences in the coupling parameters. For this reason, a single deterministic analysis is of minimal use. Therefore, the ability to determine both the ensemble average and the expected range with SEA is crucial in allowing a robust assessment of vibration transmission between plate systems with low modal density and low modal overlap.