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.     

Thermal evaluation of cashew nutshell liquid as new bioadditives for poly(methyl methacrylate)

In this study, the thermal-oxidative stability of poly(methyl methacrylate), PMMA, 1 % additivated with replenishable phenolic lipids is evaluated by thermogravimetric (TG/DTG) analyses and differential scanning calorimetry (DSC) analyses. Since technical cashew nutshell liquid (CNSL), a byproduct from the cashew industry, is composed basically of two phenolic lipids, cardanol and cardol, the utilization of this industrial waste and its main components as a new source of bioadditives for use as antioxidants is evaluated. The TG analyses revealed that addition of the phenolic constituent of CNSL increased the thermal stability of PMMA films considerably. The results obtained were also confirmed by DSC analyses.     

Engineering a Small HOMO–LUMO Gap and Intramolecular C−H Borylation by Diborene/Anthracene Orbital Intercalation

The diborene 1 was synthesized by reduction of a mixture of 1,2-di-9-anthryl-1,2-dibromodiborane(4) ( 6 ) and trimethylphosphine with potassium graphite. The X-ray structure of 1 shows the two anthryl rings to be parallel and their π(C₁₄) systems perpendicular to the diborene π(B=B) system. This twisted conformation allows for intercalation of the relatively high-lying π(B=B) orbital and the low-lying π* orbital of the anthryl moiety with no significant conjugation, resulting in a small HOMO–LUMO gap (HLG) and ultimately a C−H borylation of the anthryl unit. The HLG of 1 was estimated to be 1.57 eV from the onset of the long wavelength band in its UV/Vis absorption spectrum (THF, λ_onset=788 nm). The oxidation of 1 with elemental selenium afforded diboraselenirane 8 in quantitative yield. By oxidative abstraction of one phosphine ligand by another equivalent of elemental selenium, the B−B and C¹−H bonds of 8 were cleaved to give the cyclic 1,9-diborylanthracene 9 .     

Molecular Recognition in Glycolaldehyde,the Simplest Sugar: Two Isolated Hydrogen Bonds Win Over One Cooperative Pair

Carbohydrates are used in nature as molecular recognition tools. Understanding their conformational behavior upon aggregation helps in rationalizing the way in which cells and bacteria use sugars to communicate. Here, the simplest α-hydroxy carbonyl compound, glycolaldehyde, was used as a model system. It was shown to form compact polar C₂-symmetric dimers with intermolecular O–H⋅⋅⋅O=C bonds, while sacrificing the corresponding intramolecular hydrogen bonds. Supersonic jet infrared (IR) and Raman spectra combined with high-level quantum chemical calculations provide a consistent picture for the preference over more typical hydrogen bond insertion and addition patterns. Experimental evidence for at least one metastable dimer is presented. A rotational spectroscopy investigation of these dimers is encouraged, also in view of astrophysical searches. The binding motif competition of aldehydic sugars might play a role in chirality recognition phenomena of more complex derivatives in the gas phase.     

On the rate of convergence in the global central limit theorem for random sums of uniformly strong mixing random variables

Lithuanian Mathematical Journal - We present upper bounds of the integral $$ {\int}_{-\infty}^{\infty }{\left|x\right|}^l\left|\mathrm{P}\left\{{Z}_N0\left({S}_N{X}_1+\dots +{X}_N\right) $$ of...     

A Non-normal-mode Marginal State of Convection in a Porous Box with Insulating End-Walls

Transport in Porous Media - The 4th order Darcy–Bénard eigenvalue problem for the onset of thermal convection in a 3D rectangular porous box is investigated. We start from a recent 2D...     

Identification of Compounds that Selectively Stabilize Specific G‐Quadruplex Structures by Using a Thioflavin T‐Displacement Assay as a Tool

Small molecules are used in the G‐quadruplex (G4) research field in vivo and in vitro, and there are increasing demands for ligands that selectively stabilize different G4 structures. Thioflavin T (ThT) emits an enhanced fluorescence signal when binding to G4 structures. Herein, we show that ThT can be competitively displaced by the binding of small molecules to G4 structures and develop a ThT‐displacement high‐throughput screening assay to find novel and selective G4‐binding compounds. We screened approximately 28 000 compounds by using three different G4 structures and identified eight novel G4 binders. Analysis of the structural conformation and stability of the G4 structures in presence of these compounds demonstrated that the four compounds enhance the thermal stabilization of the structures without affecting their structural conformation. In addition, all four compounds also increased the G4‐structure block of DNA synthesis by Taq DNA polymerase. Also, two of these compounds showed selectivity between certain Schizosaccharomyces pombe G4 structures, thus suggesting that these compounds or their analogues can be used as selective tools for G4 DNA studies.