Effect of nonmesogenic impurities on the order of the nematic to smectic-A phase transition in liquid crystals

By means of adiabatic scanning calorimetry, we have studied the effect of the nonmesogenic solutes cyclohexane (CH) and biphenyl (BP) on the nematic-smectic-A phase transition in the liquid crystal octylcyanobiphenyl (8CB). For all concentrations of BP studied, the transition remains second-order. For 8CB+CH, however, crossover from second-order to first-order is observed at a tricritical point of the mole fraction x of CH around 0.0460. The difference between the two systems and the crossover is explained in terms of a mean-field free energy density expression including coupling terms of x with the nematic and smectic-A order parameters.     

Enantiomeric Separations in Capillary Electrophoresis Using 18-Crown-6-tetracarboxylic Acid (18C6H4) as Buffer Additive

An overview is presented of the applicability of the crown ether 18-crown-6-tetracarboxylic acid (18C6H₄) as buffer additive in capillary electrophoresis (CE) for the separation of enantiomers. The chiral selector 18C6H₄ is particularly useful for the separation of racemates having a primary amino function. Unfortunately, the crown ether is no longer commercially available. The synthesis and spectroscopic characterization are therefore described in detail. Moreover, a method is presented for the regeneration of the crown ether after CE application. Some new enantiomeric separations of amino acids i.e. NORLEU, ARG, GLU, m-TYR, and o-TYR are listed and the influence of the pH and temperature of the separation buffer is discussed. An intermediate in the synthetic pathway, namely 18-crown-6-tetracarboxamide, did not exhibit any enantioselectivity in CE.     

Mechanical and thermal characterization of sisal fiber reinforced polylactic acid composites

The advantages of green composites are including, but not limited to their environmental friendly nature, lightweight, reduction of production energy and costs, and recyclability. This work focuses on the mechanical, thermal, and dynamic mechanical properties of biocomposites. For that purpose, biosourced polymers were used, namely polylactic acid (PLA) and sisal fiber, and biocomposites were extruded and then injection molded with different contents of sisal fibers (5%, 10%, 15%). The results show that the increase of the rate of reinforcement improves the mechanical and dynamic mechanical properties of the biocomposites made. By the increase of the sisal fiber content, the degree of crystallinity of the matrix was increased from 47% to 61%, as sisal fibers were acted as a nucleating agent for the PLA.     

Mixed copper-lanthanide metallomesogens

This paper describes the first examples of heteropolynuclear metallomesogens that contain both a transition metal ion and a trivalent lanthanide ion. Adducts were formed between a mesomorphic [Cu(salen)] complex (salen=2,2'-N,N'-bis(salicylidene)ethylenediamine) with six terminal tetradecyloxy chains and a lanthanide nitrate (Ln=La, Gd). Different stoichiometries were found, depending on the lanthanide ion: a trinuclear copper-lanthanum-copper complex [La(NO(3))(3)(Cu(salen))(2)] and a binuclear copper-gadolinium complex [Gd(NO(3))(3)Cu(salen)]. The compounds exhibit a hexagonal columnar mesophase (Col(H)) over a wide temperature-range with rather low melting temperatures. Although the clearing point could be observed for the parent [Cu(salen)] complex, the mixed f-d complexes decomposed in the high-temperature part of the mesomorphic domain before clearing. On the basis of X-ray diffraction measurements and molecular modelling, a structural model for the mesophase of the metal complexes is proposed.     

Fast heating induced impulse halogenation of refractory sample components in electrothermal atomic absorption spectrometry by direct injection of a liquid halogenating agent

A novel electrothermal atomic absorption spectrometry (ETAAS) method was developed for the halogenation of refractory sample components (Er, Nd and Nb) of lithium niobate (LiNbO₃) and bismuth tellurite (Bi₂TeO₅) optical single crystals to overcome memory effects and carry-over. For this purpose, the cleaning step of a regular graphite furnace heating program was replaced with a halogenation cycle. In this cycle, after the graphite tube cooled to room temperature, a 20 μL aliquot of liquid carbon tetrachloride (CCl₄) was dispensed with a conventional autosampler into the graphite tube. The CCl₄ was partially dried at 80 °C under the mini-flow (40 cm³ min⁻¹) condition of the Ar internal furnace gas (IFG), then the residue was decomposed (pyrolyzed) by fast furnace heating at 1900-2100 °C under interrupted flow of the IFG. This step was followed by a clean-out stage at 2100 °C under the maximum flow of the IFG. The advantage of the present method is that it does not require any alteration to the graphite furnace gas supply system in contrast to most of the formerly introduced halogenation techniques.The effectiveness of the halogenation method was verified with the determination of Er and Nd dopants in the optical crystals. In these analyses, a sensitivity decrease was observed, which was likely due to the enhanced deterioration of the graphite tube surface. Therefore, the application of mathematical correction (resloping) of the calibration was also required. The calibration curves were linear up to 1.5 and 10 μmol L⁻¹ for Er and Nd, respectively. Characteristic masses of 18 and 241 pg and the limit of detection (LOD) values of 0.017 and 0.27 μmol L⁻¹ were found for Er and Nd, respectively. These LOD data correspond to 0.68 μmol mol⁻¹ Er and 11 μmol mol⁻¹ Nd in solid bismuth tellurite samples. The analytical results were compared with those obtained by a conventional ETAAS method and validated with X-ray fluorescence spectrometry analysis.     

Rare-earth complexes of mesomorphic Schiff's base ligands

Rare-earth complexes of mesomorphic Schiff 's bases, 4-[(alkylimino)methyl]-3-hydroxyphenyl 4-alkyloxybenzoates, were synthesized. Whereas the ligands LH display a nematic and/or a smectic C phase, the metal complexes show a viscous smectic A phase and decompose at the clearing point. The mesophase was investigated by hot-stage polarizing optical microscopy, by differential scanning calorimetry and by high temperature X-ray diffraction. Two types of complex were found, [Ln(LH)₃ (NO₃)₃] and [Ln(LH)₂L(NO₃)₂], depending on the ligand or the central metal ion. The first coordination sphere of the rare-earth ion in these metallomesogens is comparable to that in the structure of complexes with 4-alkoxy-N-alkyl2-hydroxybenzaldimine ligands.     

Modeling of the adsorption of organic compounds on polymeric nanofiltration membranes in solutions containing two compounds.

The adsorption of organic compounds in aqueous solution on polymeric nanofiltration membranes is studied; this process is one of the most important fouling mechanisms influencing the flux and retention behavior of nanofiltration membranes. It is shown that the adsorption of dissolved organic compounds on polymeric nanofiltration membranes is comparable to that on activated carbon. Freundlich and Langmuir isotherms are used to describe the relation between the adsorbed mass on the membrane and the equilibrium concentration of the organic compound in a single-compound solution. Based on these results, three models for the adsorption of solutions containing several compounds [i.e., the simple competitive adsorption model (SCAM), the model of Jain-Snoeyinck, and the model of Butler-Ockrent] were used to predict the adsorption behavior of an organic compound in an aqueous solution containing two compounds. The results of the three models were compared to experimental observations. It is shown that the SCAM allows a good prediction of the adsorption behavior.