Molecular addressing? Studies on light-induced reorientation in liquid-crystalline side chain polymers

Polarized light leads to an effective reorientation of the optic axis in the glassy state of liquid-crystalline side chain polymers containing azobenzene mesogenic groups, via a trans-cis and cis-trans isomerization. Using a combination of U V and IR dichroitic studies it is shown for copolymers consisting of chromophores (azobenzene) and non-chromophores (phenylbenzoate) that only the chromophores are reoriented by light as far as the glassy state is concerned. Individual chromophores are thus addressed by photoselection. Photoselection in the fluid nematic state, on the other hand, leads also to a reorientation of the non-chromophores.     

A calorimetric study of the different thermal behaviour of DNA in the isotropic and liquid-crystalline states

A difference between the thermal behaviour of the isotropic and liquid-crystalline state of sonicated DNA in aqueous salt solution containing poly(ethyleneglycol)(PEG) has been demonstrated. On cooling, a different degree of renaturation of thermally denaturated DNA is observed between samples which form the isotropic state and more concentrated samples which on cooling form the cholesteric state.     

Liquid crystal side chain polysiloxanes containing various proportions of non-mesogenic units

Recent studies have established that side chain polymeric liquid crystals composed of mesogenic and non-mesogenic side groups keep their liquid-crystalline properties even for a low proportion of mesogens. We show that the detailed structures of three kinds of new diluted liquid crystal polysiloxanes depend on the nature of the co-substituent as well as on the proportion of the silicon sites occupied by the mesogenic groups. Mixtures of these systems with low molar mass liquid crystals were also investigated in terms of compatibility and/or stabilization of smectic A phases.     

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.     

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     

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.     

Analysis of plane and axisymmetric flows of incompressible fluids with the stream tube method: Numerical simulation by trust-region optimization algorithm

New concepts for the study of incompressible plane or axisymmetric flows are analysed by the stream tube method. Flows without eddies and pure vortex flows are considered in a transformed domain where the mapped streamlines are rectilinear or circular. The transformation between the physical domain and the computational domain is an unknown of the problem. In order to solve the non-linear set of relevant equations, we present a new algorithm based on a trust region technique which is effective for non-convex optimization problems. Experimental results show that the new algorithm is more robust compared to the Newton-Raphson method.     

Crystallographic report: Crystal structure of tetra(4‐methyl‐5‐imidazole‐carboxyaldehyde)zinc(II) diperchlorate

The central zinc(II) atom in the title complex is tetrahedrally coordinated by four nitrogen atoms derived from 4‐methyl‐5‐imidazolecarboxyaldehyde ligands with Zn? N in the range 2.007(3) to 2.026(4) Å. Copyright © 2003 John Wiley & Sons, Ltd.     

Crystallographic report: Crystal structure of a one‐dimensional zinc(II) coordination polymer containing 4,4′‐biphenyldicarboxylate hemihydrate

A one‐dimensional zinc(II) coordination polymer has been constructed from zinc(II), 4,4′‐biphenyldicarboxylate and pyridine in which each zinc(II) atom is coordinated by two pyridine ligands and two monodentate 4,4′‐biphenyldicarboxylate ligands that define a distorted tetrahedral geometry. Copyright © 2003 John Wiley & Sons, Ltd.