Liquid crystal helical ribbons as isometric textures.

Deformations that conserve the parallelism and the distances--between layers, in smectic phases; between columns, in columnar phases--are commonplace in liquid crystals. The resulting isometric deformed textures display specific geometric features. The corresponding order parameter singularities extend over rather large, macroscopic, distances, e.g., cofocal conics in smectics. This well-known picture is modified when, superimposed to the 1D or 2D periodicities, the structure is helical. However isometry can be preserved. This paper discusses the case of a medium whose structure is made of 1D modulated layers (a lamello-columnar phase), assuming that the modulations rotate helically from one layer to the next. The price to pay is that any isometric texture is necessarily frustrated; it consists of layers folded into a set of parallel helicoids, in the manner of a screw dislocation (of macroscopic Burgers vector), the modulations being along the helices, i.e. double-twisted. The singularity set is made of two helical disclination lines. We complete this geometric analysis by a crude calculation of the energy of a helical ribbon. It is suggested that the helical ribbons observed in the B7 phase of banana-like molecules are such isometric textures. As a side result, let us mention that the description of double-twist, traditionally made in terms of a partition of the director field into nested cylinders, could more than often be profitably tested against a partition into nested helicoids.

Evidence for different polymorphisms with and without an external electric field in a series of bent-shaped molecules.

Five fluid tilted mesophases are observed in a series of achiral banana-shaped compounds. The terminal chain length is the pertinent molecular parameter which induces the polymorphism change. All the phases, refer to tilted lamellar structure without in-plane order in the layers. The observation of monolayer, bilayer, ribbon phase, and undulated structures recalls the richness of the polymorphism of the frustrated polar calamitic liquid crystals. Among the mesophases, we highlight two: a Sm-C G2 phase corresponding to a bilayer structure made of Sm-CG layers, and its two-dimensional variant, Sm- Ctilde; G2. The five mesophases observed at zero field are switchable under electric field. At least three ferroelectric phases are induced by an applied field. There is no direct correspondence between the zero field phases and the phases observed under electric field. These observations show that different polymorphisms exist in the series with and without an applied field. A unique ( E,T ) phase diagram is presented, corresponding to the superposition of the ( E,T ) diagrams obtained for each homolog of the series, where the influence of the chain length is equivalent to a shift on the temperature axis.

Textural analysis of a mesophase with banana shaped molecules.

Observed under the polarizing microscope, the B7bis phase in the banana compound D14F3 [J.P. Bedel et al., Liq. Cryst. 27, 1411 (2000)] displays two types of textures of defects, namely (a): helical ribbons, that nucleate in large quantities when the samples are quenched from a sufficiently high temperature in the isotropic phase (b)- shapes with no helicity having the structure of developable domains much akin to those observed in columnar phases, either resulting from the annealing of the helical ribbons or nucleating under slow cooling processes. The existence of these two kinds of defects points toward the complex nature of the structure of the B7 phase, which is at the same time a columnar and a smectic phase. Our observations fit the model [M. Kleman, J. Phys. France 46, 1193 (1985)] according to which the geometry of a helical ribbon is that one of the central region of a screw dislocation with a giant Burgers vector, split into two helical disclination lines of strength k = 1/2 which bound the ribbon. Textures and defects, already partly documented, and growth features and annealing processes, not yet reported in the literature, are analyzed. We conclude that the helical ribbons and the developable domains with no helicity are textures of two different B7 states, namely a metastable state and the ground state respectively. Comparative textural analysis is performed for two other banana compounds exhibiting B2 phases.

Switching of banana liquid crystal mesophases under field.

Taking advantage of the great number of bent-core or "banana" compounds synthesized and studied in the laboratory, we describe their behaviour under the application of an external electric field. If the field were a static one, we would work within the frame of an equilibrium phase diagram in a (field E, temperature T) space where some phases would be simple dielectrics and others ferroelectric ones with a macroscopic polarization, either spontaneous or induced by the field. In this paper, we deal with the basic responses of "banana" liquid crystals under the application of a low frequency (1 to 100 Hz) AC field. Firstly square-wave voltages allow us to locate the phase boundary between dielectric (at lower field) and ferroelectric phases (higher field) at a given temperature and field threshold. Then we apply slowly varying AC voltages with shapes like triangle or "triple-plateau" to check out the stability of the induced ferroelectric phase versus field removal. Three behaviours are encountered, the unstable one (short lifetime of the high-field ferroelectric phase) where the macroscopic polarization is destroyed and then rebuilt in the opposite direction during each half period and usually called "antiferroelectric"; the stable one (long lifetime) with a polarization that rotates at constant modulus which is labeled as "ferroelectric" and a new one where the macroscopic polarization is proportional to the applied field, we named this behaviour as "superparaelectric". Let us stress that these observations apply to the ferroelectric phases of the (E, T) phase diagram not to the zero field (0,T) phases observed in the usual phase characterization experiments except for an eventual spontaneous ferroelectric phase.

Liquid crystalline polymers as stationary phases. IV. Chemical bonding and immobilization of the polymer on silica characterization by solid-state nuclear magnetic resonance spectroscopy.

Chemical bonding reaction and immobilization through low energy radiation (heating) have been investigated to fix a side-chain liquid crystalline polymer (SC-LCP) on silica particles in order to use the resulting modified silica in normal-phase HPLC. Highly stable chromatographic stationary phases are observed under excellent polymer solvent flow conditions (THF) for both methods and better column efficiencies are also exhibited towards PAHs' separation compared to the classical coated stationary phase. The characterization of these new stationary phases and the rationale for improved column stability have been investigated by solid state 13C and 29Si CP/MAS NMR spectroscopy. It is clearly shown that the chemical bonding is achieved by the classical hydrosilylation reaction between PHMS chains and vinyl modified silica. The bonded polymer is likely a copolymer than a homopolymer. The immobilization of the SC-LCP by heating results in the breaking of Si-O-Si bonds of the polysiloxane chain after the attack of the silica surface silanols. Applications to fullerenes and carotenes separation of these bonded stationary phases are compared to the separation power of a classical monomeric C18 stationary phase in NP-HPLC as n-hexane-toluene or methyl-tertiobutyl ether-methanol mixtures.

Laterally attached liquid crystalline polymers as stationary phases in reversed-phase high-performance liquid chromatography. V. Study of retention mechanism using linear solvation energy relationships.

A linear solvation energy relationship model was used to characterize the retention behavior of a stationary phase based upon a nematic side-on liquid crystalline polymer (SOLCP) in reversed-phase liquid chromatography. The set of solutes was constituted of a high variety of compounds whose molecular sizes were considerably smaller than the mesogenic unit size. The results showed good statistical fits for these retention data in 65:35, 75:25 and 85:15 (v/v) methanol-water mobile phases. Both the cavity term and excess molar refraction are the most important favorable retention-governing parameters, whereas the solute hydrogen bond acceptor basicity is the most unfavorable retention parameter. Hydrophobicity and pi-pi interactions decrease strongly when the percentage of methanol increases, leading to an important retention decrease despite the fact that the hydrogen bond interaction weakens as the organic solvent is added. The shape recognition ability of this side-on liquid crystalline stationary phase on polycyclic aromatic hydrocarbon solutes is partly explained by the solutes' high polarizability due to the presence of pi-electrons. However, the solute polarizability is not sufficient and a stationary phase's "structure effect" must to be taken into account for the shape discrimination observed. The strong interaction between liquid crystal molecules caused likely a adsorption retention mechanism rather than a partition mechanism.

Laterally attached liquid-crystalline polymers as stationary phases in reversed-phase high-performance liquid chromatography. III. Effect of the local anisotropic order on the separation of polycyclic aromatic hydrocarbons.

Specific stationary phases based upon non-liquid-crystalline polymers, liquid-crystalline molecules and side-on fixed liquid-crystalline polymers (SO-LCP) have been synthesized for use as silica modified stationary phases in high-performance liquid chromatography (HPLC). The mesogenic side group of the SO-LCP was composed of three phenyl ring benzoate type with terminal alkoxy chains and was laterally linked to a polysiloxane backbone via an alkyl ester spacer arm. This study demonstrated that the shape recognition of stationary phases based upon SO-LCP towards the length-to-breath ratio (L/B) was strongly connected to the existence of a local liquid-crystalline order into the pores of silica gel, warranting the interest of the collective organization of mesomorphic materials in liquid chromatography. Furthermore, the chromatographic performances depended on the kind of anisotropic order and it was more advantageous to use smectic side-on liquid-crystalline polymer than nematic and obviously non-liquid-crystalline ones. Finally, for a series of polymers having the same mesomorphism, the larger the temperature stability range of the mesophase, the more pronounced the local order effect and the higher the shape recognition.

Laterally attached liquid crystalline polymers as stationary phases in reversed-phase high-performance liquid chromatography. II. Optimization of the molecular parameter of the polymer.

Stationary phases obtained by coating side-chain liquid crystalline polymers (LCPs) with the mesogenic rod like units laterally attached to a polysiloxane backbone via a flexible spacer have been already reported. These phases show excellent planarity and shape recognition for polynuclear aromatic hydrocarbon (PAH) solutes in reversed-phase liquid chromatography. Optimization of these stationary phases in terms of molecular parameters of the polymer is here described. Fifteen stationary phases have been prepared varying different parameters such as the spacer length, the aliphatic tail length, and the proportion of laterally attached mesogenic units along the polymer chain. The results show that the combination of a long spacer and long terminal chains, which generates a smectic phase in the polymer bulk, leads to the best chromatographic performances towards planarity and shape recognition for PAH solutes.

Investigation of the nematic-isotropic transition of a liquid crystalline polymer and determination of molecular diffusion coefficients using gas chromatography.

Inverse gas chromatography has been used to study the nematic-isotropic transition of a side chain liquid crystalline polymer (LCP). The mesogenic side groups are laterally attached to a polysiloxane backbone through a flexible spacer. The nematic-isotropic transition of this LCP coated onto a glass capillary column is detected by considering the variation with temperature of the retention volume and of the theoretical plate number for the several probes. The molecular diffusion coefficients, D, of naphthalene, fluorene, pyrene and o-terphenyl have been determined at different temperatures in the nematic phase of the LCP as well as in the isotropic melt. The values ranged between 10(-14) and 10(-12) m2 s(-1) for the polynuclear aromatic hydrocarbon probes tested.