Liquid crystalline behaviour from binary mixtures of non-mesogenic 4-alkyl-N-(4-cyanophenyl) piperidines [1]

A relatively rare phenomenon, the induction of thermotropic mesophases from combinations of homologues of non-mesogenic compounds, is examined in some detail. Thus, monotropic nematic phases have been obtained from binary mixtures of 4-alkyl-N-(4-cyanophenyl)piperidines (I). Except for the hexyl homologue, the compounds I with butyl to nonyl as alkyl groups are non-mesomorphic as neat materials. From phase diagrams, the nematic clearing temperatures of the binary mixtures are found to vary linearly with composition and to increase as the molecular lengths of the components are increased. By introducing a methyl group at the 1-position of the alkyl chain, the melting points of the neat components are depressed, and the nematic clearing temperatures of the binary mixtures are lowered. Factors associated with the induction of this mesomorphism and with the 'kinetic' and thermodynamic stabilities of the monotropic nematic phases are discussed. Among these is the orientation between the rings of the core groups in I and in the more common mesogens, the trans-4-alkyl-1-(4-cyanophenyl) cyclohexanes, II.     

Manifestation of biquadratic coupling in the smectic C* phase soft mode dielectric response

The soft mode dielectric response of three ferroelectric chiral smectic C* substances is studied in the vicinity of the smectic C*-smectic A* phase transition. For some substances the soft mode dielectric strength exhibits a pronounced anomaly in the C* phase just below the phase transition. We show how this anomaly can be systematically correlated with a corresponding anomaly in the experimentally determined ratio of spontaneous polarization over tilt. By comparing the experimental results with the theoretical predictions of an extended Landau model, we demonstrate how the crossover behaviour of the system can be interpreted as being the consequence of the presence of a biquadratic coupling between tilt and polarization in the Landau free-energy of the system.     

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.     

Amending cultures of selenium-resistant bacteria with dimethyl selenone

A possible biological intermediate in the reduction and methylation of selenium oxyanions, dimethyl selenone, was synthesized, and the first experiments involving the amendment of selenium resistant bacterial cultures with this compound are reported. The amount of volatile, reduced selenium-containing species released from these cultures into the headspace is significantly more than that produced in analogous experiments involving sodium selenate amended cultures. Dimethyl selenone is reduced in the presence of dimethyl sulfide and dimethyl disulfide in a complex growth medium, trypticase soy broth with 0.1% nitrate. This reduction occurs whether or not the reduced sulfur compounds are biologically produced.     

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.     

Gas-phase thermal decomposition of peroxy-N-butyryl nitrate

The gas-phase thermal decomposition rate of peroxy-n-butyryl nitrate (n-C₃H₇C(O)OONO₂, PnBN) has been measured at ambient temperature (296 K) and 1 atm of air relative to that of peroxyacetyl nitrate (CH₃C(O)OONO₂, PAN) using mixtures of PAN (14–19 ppb), PnBN (22–46 ppb), and nitric oxide (1.35–1.90 ppm). The PnBN/PAN decomposition rate ratio was 0.773 ± 0.030. This ratio, together with a literature value of 3.0 × 10^?4 s^?1 for the thermal decomposition rate of PAN at 296 K, yields a PnBN thermal decomposition rate of (2.32 ± 0.09) × 10^?4 s^?1. The results are briefly discussed by comparison with data for other peroxyacyl nitrates and with respect to the atmospheric persistence of PnBN. © 1994 John Wiley & Sons, Inc.     

Temperature-dependent behavior of birefringence and rotation of the optical indicatrix in crystals of deuterated triglycinesulfate

On the basis of a complex null-polarimetric method, the natural birefringence and the rotation of the optical indicatrix in crystals of deuterated triglycinesulfate are measured in the temperature range of 300–340 K. The temperature-dependent behavior of the optical parameters is shown to be close to that observed previously in triglycinesulfate crystals. Changes in them upon the ferroelectric phase transition can be accounted for by the spontaneous quadratic electro-optic effect, with the values of the electro-optic coefficients being larger by a factor of 1.4 than in triglycinesulfate crystals.     

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.