Large flow birefringence of nematogenic bent-core liquid crystals.

We have found that bent-core liquid crystalline materials show exceptionally large intrinsic flow birefringence in their isotropic liquid phase. This effect is more than 100 times larger than typical values measured for low molecular weight liquid crystals. The specific flow birefringence (i.e., normalized by the flow viscosity) is an order of magnitude larger than in both side-chain polymeric as well as low molecular weight liquid crystals. We propose that this large enhancement for bent-core compounds may be attributed to nanoscale smecticlike clusters that persist above the nematic-isotropic transition temperature, and shear align under shear flow; however, this mechanism has not yet been definitively confirmed.

Polarization splay as the origin of modulation in the B1 and B7 smectic phases of bent-core molecules.

We report a generalized scenario for the formation of modulated smectic phases of bent-core molecules based on locally ferroelectric layering and spontaneous splay of the polarization. Twelve phases are proposed, distinguished by neighboring splay stripes with either syn- or antiorder of the polarization and undulation slope, in addition to layer continuity versus layer discontinuity at the intervening defects. We outline the experimental techniques necessary to differentiate among the phases and interpret previous results in the present context, using high resolution x-ray scattering diffraction and block and undulation models of the layer organization to distinguish among the three 2D lattice types which emerge.

The structural transitions in 6CHBT-based ferronematic droplets.

In this work we describe the observations of structural transitions in ferronematics based on the thermotropic nematics 6CHBT (4-trans-4'-n-hexyl-cyclohexyl-isothiocyanato-benzene). The ferronematic droplets were observed in solutions of nematogenic 6CHBT dissolved in phenyl isocyanate and doped with fine magnetic particles. The phase diagram of the transitions from the isotropic phase to the nematic phase via a droplet state was found. Magneto-dielectric measurements of various structural transitions in this new system enabled us to estimate the type of anchoring of the nematic molecules on the magnetic particle surfaces in the droplets.

Giant flexoelectricity of bent-core nematic liquid crystals.

Flexoelectricity is a coupling between orientational deformation and electric polarization. We present a direct method for measuring the flexoelectric coefficients of nematic liquid crystals (NLCs) via the electric current produced by periodic mechanical flexing of the NLC's bounding surfaces. This method is suitable for measuring the response of bent-core liquid crystals, which are expected to demonstrate a much larger flexoelectric effect than traditional, calamitic liquid crystals. Our results reveal that not only is the bend flexoelectric coefficient of bent-core NLCs gigantic (more than 3 orders of magnitude larger than in calamitics) but also it is much larger than would be expected from microscopic models based on molecular geometry. Thus, bent-core nematic materials can form the basis of a technological breakthrough for conversion between mechanical and electrical energy.

13C and 2H NMR study of structure and dynamics in banana B2 phase of a bent-core mesogen.

In this paper, the difficulty in orienting the B(2) phase of the banana mesogen 1,3-Phenylene-bis 4-[4-(10-undecenyloxy)-benzoyloxy] benzoate (Pbis11BB) in a relatively high magnetic field is reported based on some observations using both (13)C and (2)H NMR. (2)H NMR spectra recorded for the two labeled isotopomers of Pbis11BB in the isotropic and B(2) phases are shown here. Preliminary results on the deuteron spin-spin relaxation (T(2)) data are reported at 61 MHz in order to underline the peculiar slow dynamics of banana-shaped liquid crystals (BLC), and these results are discussed in the framework of recent studies on similar BLC. The molecular structure and dynamics in the B(2) and crystalline phases are also studied by (13)C solid-state NMR techniques. The results also point to the slow dynamics in the B(2) phase of Pbis11BB. In particular, two-dimensional MAS exchange experiment has been performed to shed light on the molecular conformation structure of the five-ring banana core in the crystalline phase of Pbis11BB, and to compare with that of quantum mechanical calculations reported in the literature.

Critical behavior at the isotropic-to-nematic phase transition in a bent-core liquid crystal.

Magnetic birefringence and dynamic light scattering measurements of orientational order parameter fluctuations at the isotropic-nematic phase transition of a bent-core liquid crystal reveal a pretransitional temperature dependence consistent with the standard Landau-deGennes mean field theory. However, as follows: the transition in the bent-core compound is more weakly first order (TNI-T* approximately 0.4 degrees C), the leading Landau coefficient is approximately 30 times lower, the viscosity associated with nematic order fluctuations is approximately 10 times higher, and the density change is approximately 10 times lower, than typically observed in calamitic (rod-shaped) liquid crystals. One consistent explanation for these anomalies is an optically isotropic phase composed of microscopic complexes or "clusters" of bent-core molecules.

Nonstandard electroconvection in a bent-core nematic liquid crystal.

We characterize three nonstandard electrohydrodynamic instabilities in nematic liquid crystals composed of bent-core molecules. In addition to their shape, another important attribute of this material is that the anisotropy in the electrical conductivity changes sign as the frequency of the applied electric field changes. These instabilities do not appear to fit within the standard model for electroconvection. The first instability creates a pattern with stripes parallel to the initial director orientation, with a wavelength about equal to the separation of the cell plates. The next is the previously reported prewavy instability. The third instability is optically and dynamically identical to the prewavy instability, but is distinguished by different threshold behavior.

Orientational ordering of a bent-core mesogen by two-dimensional 13C NMR spectroscopy.

Various two-dimensional (2D) NMR techniques are reported on a bent-core mesogen 4,6-dichloro-1,3-phenylenebis[4'-(9-decenyloxy)-1,1'-biphenyl] carboxylate in its nematic and solid phases in order to unambiguously assign its carbon-13 NMR spectrum. The (13)C chemical shifts from the molecular core were studied as a function of temperature to extract its molecular geometry and orientational order tensor. To this end, the chemical shift anisotropy tensors of some carbon sites were measured in the solid state of this mesogen using a recent method called the separation of undistorted powder patterns by effortless recoupling (SUPER). The average bending angle subtended by the two arms of the bent-core structure is determined to be 148.7 degrees. The C-H dipolar couplings obtained from the separated local field (SLF) experiment for the aromatic rings are used to find the local order parameter tensors.

Structure and order of a homologous series of bent-core molecules: a 13C NMR study.

A carbon-13 NMR study in a series of bent-core (banana-shaped) molecules is reported. In 1, 3- phenylene bis[4'-alkenyloxy biphenyl]-4-carboxylate derivatives the position of the chlorine substituent(s) connected to the central phenyl ring and/or the terminal chain length of the compounds were varied. By analyzing the observed chemical shift anisotropies, the order parameters S and bending angles in their nematic phase are compared. The biphenyl moiety on each arm of the molecular core is found to form a nonzero twist angle.

Characterization of reaction products formed during thin-layer chromatographic detection of thiocarbamate herbicides.

The reaction between thiocarbamate herbicides and 2,6-dichlorobenzoquinone-N-chloroimine or 2,6-dibromobenzoquinone-N-chloroimine is suitable for the detection of these herbicides on thin-layer plates with high sensitivity. The reactions were followed by infrared, nuclear magnetic resonance and mass spectrometry. We have established the formation of 2,6-dichlorobenzoquinone-S-alkyl sulphenylimines. In the case of the bromo-derivative, halogen exchange and substitution on the quinone ring took place simultaneously leading to the formation of mixed halogenated 2,6-dihalo- and, in addition, 2,3,6-trihalobenzoquinone-S-alkyl sulphenylimines. The final product of the detection reaction, i.e. 2,6-dichlorobenzoquinone-S-alkyl sulphenylimine was reacted with 2,6-dibromobenzoquinone-N-chloroimine where 2,6-dichloro-3-bromobenzoquinone-S-alkyl sulphenylimine formed as a consequence of the looser bromine-carbon linkage on the 2 and 6 positions of the quinone ring.

Chromatographic methods for the determination of pesticides in foods.

Chromatography is the most important technique available to the analyst dealing with the determination of pesticide residues in food, feed and environmental samples. Numerous methods for pesticide residues in foods have been developed in the past few years, and this paper reviews some of the most important procedures. A great variety of chromatographic methods, such as solid-phase extractions, column chromatographic clean-up methods, thin-layer, gas, high-performance liquid and supercritical fluid chromatography, and their coupling with sensitive and selective detection methods are surveyed.

Selectivity and sensitivity of some thin-layer chromatographic detection systems.

The selectivity and sensitivity of some thin-layer chromatographic detection systems widely used internationally and developed in our laboratory were studied. Halogenated organophosphorus pesticides were found to interfere with the detection of organochlorine pesticides when using silver nitrate-2-phenoxyethanol. The stability of colours formed by the 4-(4'-nitrobenzyl)pyridine-tetraethylenepentamine system was enhanced by spraying with acetic acid and allowed densitometric evaluation. The most sensitive detection method for thiocarbamates is the reaction with 2,6-dichlorobenzoquinone-N-chloroimine or its dibromo analogue (50 ng). Application of this method for sulphur-containing organophosphorus insecticides results in the same or better sensitivity. Quantitation of these compounds was carried out by densitometry.