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.     

The nitrogen pentoxide dissociation equilibrium

The third-law method is used to assess the authenticity of available equilibrium constants for the thermal dissociation of N₂O₅ ? NO₂ + NO₃. © 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.     

Elevation of the glass transition temperature in flexible‐chain semicrystalline polymers

In the idealized two‐phase model of a semicrystalline polymer, the amorphous intercrystalline layers are considered to have the same properties as the fully‐amorphous polymer. In reality, these thin intercrystalline layers can be substantially influenced by the presence of the crystals, as individual polymer molecules traverse both crystalline and amorphous phases. In polymers with rigid backbone units, such as poly(etheretherketone), PEEK, previous work has shown this coupling to be particularly severe; the glass transition temperature (T_g) can be elevated by tens of degrees celsius, with the magnitude of the elevation correlating directly with the thinness of the amorphous layer. However, this connection has not been explored for flexible‐chain polymers, such as those formed from vinyl‐type monomers. Here, we examine T_g in both isotactic polystyrene (iPS) and syndiotactic polystyrene (sPS), crystallized under conditions that produce a range of amorphous layer thicknesses. T_g is indeed shown to be elevated relative to fully‐amorphous iPS and sPS, by an amount that correlates with the thinness of the amorphous layer; the magnitude of the effect is severalfold less than that in PEEK, consistent with the minimum lengths of polymer chain required to make a fold in the different cases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1198–1204, 2007     

Transformations of cobalt trimethylacetate complexes with pyrazole upon oxidation by air in THF

Synthetic routes to oxidation of cobalt atoms in cobalt trimethylacetate complexes containing coordinated pyrazole molecules have been considered.     

Asymptotics of a multiple Cauchy integral with rapidly oscillating exponential

An asymptotic expansion uniform with respect to a parameter is obtained for a multiple Cauchy integral with a rapidly oscillating exponential in the integrand under the assumption that the singularity lines are in a general position.Translated fromMatematicheskie Zametki, Vol. 58, No. 2, pp. 231–242, August, 1995.The work was financially supported by the Russian Foundation for Basic Research under grant No. 94-01-00193-a.     

Smectic liquid-crystalline phases of F(CF2)7(CHOH)(CH2)8H and F(CF2)9(CHOH)(CH2)10H Comparison with other partially fluorinated molecules

Partially fluorinated alcohols F(CF₂)_m(CHOH)(CH₂)_nH (where m = 7, n = 8 and m = 9, n = 10) exhibit highly ordered smectic liquid-crystalline phases, as confirmed by optical microscopy and differential scanning calorimetry. Miscibility studies show that the smectic phases of the two alcohols are not of the same type. The related partially fluorinated ketones F(CF₂)_mCO(CH₂)_nH do not form a detectable mesophase. This is rather surprising since the (more polar) corresponding alcohols and the (less polar) analogous iodides and n-alkanes do. A brief discussion of the results and a comparison among partially fluorinated alkanes with various functional groups are presented.     

Neighborhood unions and the cycle cover number of a graph

For several years, the study of neighborhood unions of graphs has given rise to important structural consequences of graphs. In particular, neighborhood conditions that give rise to hamiltonian cycles have been considered in depth. In this paper we generalize these approaches to give a bound on the smallest number of cycles in G containing all the vertices of G. We show that if for all x, y ? V(G), |N(x) ∩ N(y)| ≧ 2n/5 + 1, then V(G) is coverable by at most two cycles. Several related results and extensions to t cycles are also given.