Crystal Engineering of Supramolecular 1,4-Benzene Bisamides by Side-Chain Modification – Towards Tuneable Anisotropic Morphologies and Surfaces

Benzene bisamides are promising building blocks for supramolecular nano-objects. Their functionality depends on morphology and surface properties. However, a direct link between surface properties and molecular structure itself is missing for this material class. Here, we investigate this interplay for two series of 1,4-benzene bisamides with symmetric and asymmetric peripheral substitution. We elucidated the crystal structures, determined the nano-object morphologies and derived the wetting behaviour of the preferentially exposed surfaces. The crystal structures were solved by combining single-crystal and powder X-ray diffraction, solid-state NMR spectroscopy and computational modelling. Bulky side groups, here t-butyl groups, serve as a structure-directing motif into a packing pattern, which favours the formation of thin platelets. The use of slim peripheral groups on both sides, in our case linear perfluorinated, alkyl chains, self-assemble the benzene bisamides into a second packing pattern which leads to ribbon-like nano-objects. For both packing types, the preferentially exposed surfaces consist of the ends of the peripheral groups. Asymmetric substitution with bulky and slim groups leads to an ordered alternating arrangement of the groups exposed to the surface. This allows the hydrophobicity of the surfaces to be gradually altered. We thus identified two leitmotifs for molecular packings of benzene bisamides providing the missing link between the molecular structure, the anisotropic morphologies and adjustable surface properties of the supramolecular nano-objects.     

Preparation and characterization of fibres from a thermotropic liquid crystal polyester with non-coplanar biphenylene units

Abstract

Fibres were prepared from the nematic melt of poly(2,2′-dimethyl-4,4′-biphenylene phenylterephthalate). The phenyl substitution in the terephthalic acid moiety in combination with the non-coplanar biphenyl moiety prevent crystallization of this thermotropic polyester. Oriented fibres were prepared by two different methods. Similarly to other thermotropic liquid crystal polymer fibres, chain orientation can be achieved by an elongational flow in a down draw process. This polyester also allows tensile deformation of the spun fibres around the glass transition temperature. In both routes similar degrees of orientation and mechanical properties were obtained. Tensile moduli in the order of 40–45 GPa and tensile strengths up to 550–650 MPa were obtained. The orientation function values were determined to be in the order of 0·8–0·9. A comparison with other unsubstituted thermotropic liquid crystal polyesters at the same level of orientation revealed that the moduli are the same, although the substituents increase the chain diameter. This result may be attributed to an increase of the apparent shear modulus due to an interlocking mechanism of the rigid lateral substituents.     

Polymer electrolytes—relaxation and transport properties

Relaxations in polymer electrolytes were studied in poly(ethylene oxide) and epoxidized natural rubbers both filled with lithium perchlorate. Impedance relaxation was investigated over a wide range of salt concentration at room temperature. Imaginary part of impedance as a function of frequency exhibits generally one maximum and one minimum. These two extreme values rule properties in the DC limit. They can be related to transport properties and degree of dissociation. It turns out that DC conductivity is dominantly ruled by transport coefficient.     

Turbulence structure of dilute polymer and surfactant solutions in artificially roughened pipes

Pressure drop and velocity profile measurements are presented for turbulent flows of drag reducing fluids. The investigation was done in two rough pipes, known as k- and d-type rough pipes. The results are compared with those obtained in hydraulically smooth pipe of identical diameter. The spatial arrangement of the roughness elements in the pipe determines the parallel shift in the elastic sublayer and in the core region of the dimensionless turbulent velocity profile. The slopes of the velocity profiles in these regions remain unaffected by the arrangement which is an indication that the hydrodynamic influence of the roughness is restricted to the near-wall region. The drag reducing surfactant solution exhibited a drag reduction in the smooth as well as in the rough pipes which was higher than that given by Virk's maximum drag reduction asymptote. For this solution no influence of the roughness on the turbulence was detected when the dimensionless roughness height in viscous units was less than 12.     

Phase Behavior of Polymer Blends

Major emphasis is placed on the phase behavior of miscible polymer blends. To understand the complex phase behavior of blends, a refined version of an equation-of-state theory is discussed. This theory makes the simultaneous occurrence of upper critical solution temperature and lower critical solution temperature in blends of high molar mass polymers conceivable. The kinetics of isothermal phase dissolution as it emanates from different experimental routes is discussed in terms of CahN′s linearized theory of phase separation. The rate of phase dissolution varies as a function of quench depth, which indicates the rate is directed by both the thermodynamic driving force and the mobility.     

IndecomposableA-module summands inH * V which are unstable algebras

Letp be a prime and denote byA the modp Steenrod algebra. We determine the indecomposableA-module summands ofH*((ℤ/p)) ^d ;F _p which admit the structure of an unstableA-algebra. In fact, it turns out that this is equivalent to the problem of determining those indecomposableA-module summands which arise as the modp cohomology of a space (or even a classifying space of a finite group). We reduce this problem to one in modular representation theory, namely for whichd andp is the projective cover of the trivial one dimensional GL(d,F _p ) representationF _p a permutation module. Our solution of this latter problem makes use of the classification of subgroups of GL(d,F _p ) acting transitively on (F _p ) ^d \{0} and hence depends on the classification of finite simple groups (on Feit-Thompson's odd order theorem ifp=2).     

Synthesis and characterization of a semiflexible liquid crystalline polyester with a broad nematic region

In this paper, we report on the synthesis and detailed characterization of a new semiflexible nematic liquid crystalline polyester which could serve as a 'model' polyester for a variety of physical and physico-chemical investigations. The polymer is a nematic liquid over a wide temperature range-from the glass transition temperature at ∼95°C to the isotropic transition at ∼240°C. We expect this polyester to be particularly useful for studying the effect of flow on the orientation of liquid crystalline polymers, as well as the production and removal of disclinations.