Lyotropic liquid crystalline phases formed in an ionic liquid

Lyotropic liquid crystalline phases of an amphiphilic block copolymer are constructed and characterized in an ionic liquid with comparison of component and temperature effects.     

New liquid crystalline phases with layerlike organization

Novel lamellar mesophases which are quite distinct from conventional smectic mesophases were obtained with a bolaamphiphilic triblock molecule composed of a rigid biphenyl core, two polar 2,3-dihydroxypropoxy groups in the terminal 4- and 4'-positions, and a semiperfluorinated chain [O(CH2)6C10F21] in the lateral 3-position. The competitive combination of microsegregation and rigidity in this molecule leads to layer structures in which the bolaamphiphilic cores segregate from the lateral chains into distinct sublayers. In these sublayers the biphenyl cores are aligned parallel to the layer planes. Decreasing the temperature leads to a subsequent inset of orientational and positional order of the biphenyl unit, which leads to a transition from an uniaxial SmA phase to a biaxial SmAb phase and finally to a mesophase with an additional periodicity within the aromatic sublayers. Here, microsegregation occurs on two distinct levels: The segregation of the nonpolar chains from the aromatic cores leads to the "bulk" layer structure and segregation of polar and aromatic subunits within the aromatic sublayers gives rise to an additional periodicity within the aromatic sublayers. These phases can be regarded as smectic phases built up by quasi-2D layers with nematic, respectively SmA-like order, separated by isotropic layers of the lateral chains.     

Reactivity within smectic B liquid crystalline phases

ASE quaternization reaction is used as reactivity probe within Sm B solvents. The aim of the present study was that of investigating, by means of many physical techniques (DSC calorimetry, Optical Microscopy, X-ray diffraction. Kinetic measurements and Linear Dichroism), the profound differences which occur in a reaction carried out in “internally non-homogeneous” smectic phases with respect to “internally homogeneous” media, such as isotropic, nematic or cholesteric solvents.The Linear Dichroism technique proved particularly valuable in this regard because it displayed multisite distribution of the solute reactant molecules within the SmB solution. This observation provides a unifying framework explaining the experimental data from all the different physical techniques employed.     

Emulsified microemulsions and oil-containing liquid crystalline phases

Self-assembled nanostructures, such as inverted type mesophases of the cubic or hexagonal geometry or reverse microemulsion phases, can be dispersed using a polymeric stabilizer, such as the PEO-PPO-PEO triblock copolymer Pluronic F127. The particles, which are described in the present study, are based on monolinolein (MLO)-water mixtures. When adding tetradecane (TC) to the MLO-water-F127 system at constant temperature, the internal nanostructure of the kinetically stabilized particles transforms from a Pn3m (cubosomes) to a H2 (hexosomes) and to a water-in-oil (W/O, L2) microemulsion phase (emulsified microemulsion (EME)). To our knowledge, this is the first time that the formation of stable emulsified microemulsion (EME) systems has been described and proven to exist even at room temperature. The same structural transitions can also be induced by increasing temperature at constant tetradecane content. The internal nanostructure of the emulsified particles is probed using small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM). At each investigated composition and temperature, the internal structure of the dispersions is observed to be identical to the corresponding structure of the nondispersed, fully hydrated bulk phase. This is clear evidence for the fact that the self-assembled inner particle nanostructure is preserved during the dispersion procedure. In addition, the internal structure of the particles is in thermodynamic equilibrium with the surrounding water phase. The internal structure of the dispersed, kinetically stabilized particles is a "real" and stable self-assembled nanostructure. To emphasize this fact, we denoted this new family of colloidal particles (cubosomes, hexosomes, and EMEs) as "ISASOMES" (internally self-assembled particles or "somes").     

Highly fluorescent crystalline and liquid crystalline columnar phases of pyrene-based structures

A concept for highly ordered solid-state structures with bright fluorescence is proposed: liquid crystals based on tetraethynylpyrene chromophores, where the rigid core is functionalized with flexible, promesogenic alkoxy chains. The synthesis of this novel material is presented. The thermotropic properties are studied by means of differential scanning calorimetry (DSC), cross-polarized optical microscopy (POM), and X-ray diffraction. The mesogen possesses an enantiotropic Col(h) phase over a large temperature range before clearing. The material is highly fluorescent in solution and, most remarkably, in the condensed state, with a broad, strongly red shifted emission. Fluorescence quantum yields (Phi(F)) have been determined to be 70% in dichloromethane solution and 62% in the solid state. Concentration- and temperature-dependent absorption and emission studies as well as quantum-chemical calculations on isolated molecules and dimers are used to clarify the type of intermolecular interactions present as well as their influence on the fluorescence quantum yield and spectral properties of the material. The high luminescence efficiency in the solid state is ascribed to rotated chromophores, leading to an optically allowed lowest optical transition.     

Columnar phases of achiral vanadyl liquid crystalline complexes

Two liquid crystalline vanadyl complexes have been studied by frequency domain dielectric spectroscopy over the range 10 mHz to 13 MHz. The materials exhibit two or three columnar phases denoted Col_ro, Col_rd, and Col_hd that were identified by X-ray diffraction. In the higher temperature Col_rd phase, a relaxation process in the kHz range is observed that is attributed to the reorientation about the molecular short axis. A pronounced dielectric relaxation process shows up in the low temperature Col_ro phase at hertz and sub-hertz frequencies. This slow relaxation is assigned to reorientation of the molecular dipoles within the polar linear chains, which are aligned along the column's axis. Triangular wave switching studies at low frequency reveal processes inside the Col_ro phase which are most probably due to ionic/charges relaxations but a ferroelectric switching for an achiral discotic system cannot be ruled out completely. Below the Col_ro phase there is an orientationally disordered crystalline Cr_x phase with disordered side chain dipoles. A dielectric relaxation process connected with the intramolecular relaxation of the alkoxy side chains, similar to the beta-process of polymers, has been found in the lower temperature Cr_x phase.     

Polymorphism of natural fatty acid liquid crystalline phases

We study the phase behavior in water of a mixture of natural long chain fatty acids (FAM) in association with ethylenediamine (EDA) and report a rich polymorphism depending on the composition. At a fixed EDA/FAM molar ratio, we observe upon dilution a succession of organized phases going from a lamellar phase to a hexagonal phase and, finally, to cylindrical micelles. The phase structure is established using polarizing microscopy, SAXS, and SANS. Interestingly, in the lamellar phase domain, we observe the presence of defects upon dilution, which SAXS shows to correspond to intrabilayer correlations. NMR and FF-TEM techniques suggest that these defects are related to an increase in the spontaneous curvature of the molecule monolayers in the lamellae. ATR-FTIR spectroscopy was also used to investigate the degree of ionization within these assemblies. The successive morphological transitions are discussed with regards to possible molecular mechanisms, in which the interaction between the acid surfactant and the amine counterion plays the leading role.     

Columnar phases of achiral vanadyl liquid crystalline complexes

Two liquid crystalline vanadyl complexes have been studied by frequency domain dielectric spectroscopy over the range 10 mHz to 13 MHz. The materials exhibit two or three columnar phases denoted Col_ro, Col_rd, and Col_hd that were identified by X-ray diffraction. In the higher temperature Col_rd phase, a relaxation process in the kHz range is observed that is attributed to the reorientation about the molecular short axis. A pronounced dielectric relaxation process shows up in the low temperature Col_ro phase at hertz and sub-hertz frequencies. This slow relaxation is assigned to reorientation of the molecular dipoles within the polar linear chains, which are aligned along the column's axis. Triangular wave switching studies at low frequency reveal processes inside the Col_ro phase which are most probably due to ionic/charges relaxations but a ferroelectric switching for an achiral discotic system cannot be ruled out completely. Below the Col_ro phase there is an orientationally disordered crystalline Cr_x phase with disordered side chain dipoles. A dielectric relaxation process connected with the intramolecular relaxation of the alkoxy side chains, similar to the beta-process of polymers, has been found in the lower temperature Cr_x phase.     

Field-induced reorientation dynamics in liquid crystalline hexatic phases

A smectic hexatic phase with tilted molecules is assumed to be confined between two plane boundaries. At a finite boundary distance two dielectric modes are excited by an a.c. external electric field. Using the elastic continuum theory, equations for the relaxation times and the corresponding dielectric susceptibilities are derived and discussed in the limit of high boundary distances and for different material parameters.     

The structure of 2,2'-difluorobiphenyl in solid crystalline and liquid crystalline phases

The structure of 2,2-difluorobiphenyl in the solid, crystalline phase has been determined by X-ray diffraction. In this phase the molecules are all in a single conformation having the two fluorine nuclei in a syn -arrangment, with the two ring normals at 58 to one another. The structure of the same molecule, but dissolved in a liquid crystalline solvent has been investigated by NMR spectroscopy. In the liquid crystalline phase there is rotation about the inter-ring bond through an angle phi , with a probability distribution P(phi) which has an absolute maximum at the syn-form with phi about 51 . There is also a second maximum in P(phi) at about 130 , corresponding to the anti-form. The syn- and anti-forms are present in the approximate ratio 0.58:0.42.     

Study of the liquid crystalline phases of benzopurpurin in water

We report the NMR study of the liquid crystalline phases of aqueous solutions of the dye benzopurpurin (BP-4B). Upon changing dye concentration, the system exhibits a phase transition between two ordered phases at about 3·5 wt %. The structure of these phases was not determined but the evidence suggests that they consist of columns or helically twisted columns of stacked dye molecules which are randomly oriented, similar to nematic phases.     

Thermotropic and lyotropic liquid crystalline phases of rigid aromatic amphiphiles

Rodlike amphiphilic molecules that contain exclusively aromatic building-blocks and no flexible alkyl chains have been synthesized and their mesomorphic properties investigated. These novel compounds bear diol head groups of different size (2,3-dihydroxypropyloxy or 5,6-dihydroxy-3-oxahexyloxy groups) at one end of a biphenyl unit, various aromatic segments (benzyloxy, 4-, 3-, or 2-methylbenzyloxy, phenoxy groups) at the other, and additional methyl substituents in different positions. They were synthesized by using Suzuki cross-coupling reactions as the key steps. Their thermotropic mesomorphism was investigated by means of polarized light optical microscopy, differential scanning calorimetry, and, for enantiotropic phases, by X-ray scattering. The liquid crystallinity of this class of compounds is influenced by protic solvents, such as water and glycerol. Dependent on the temperature and the solvent content, different SA phases were found. Several mesophases resulting from the frustration of these layer structures (e.g., different columnar phases, optical isotropic mesophases, and nematic phases) were also present. The smectic phases have different degrees of intercalation (SAd, SA2). The columnar phases are supposed to be ribbon structures that result from the collapse of the smectic layers. They occur in some pure compounds or they are induced upon the addition of protic solvents. The particular phase sequences of the different compounds depend mainly on the position of the methyl substituents at the biphenyl cores and are largely determined by the degree of intercalation of the aromatic cores.     

Stable liquid crystalline phases of colloidally dispersed exfoliated layered niobates

Colloidally dispersed niobium oxide nanosheets obtained by exfoliation of layered niobates HNb(3)O(8) and HTiNbO(5) formed stable liquid crystalline phases; their liquid crystallinity was dependent on the niobate species exfoliated.     

Growth dynamics of CdTe nanoparticles in liquid and crystalline phases

Normally the size dependence of the chemical potential is used to explain the growth dynamics of semiconductor nanoparticles. Instead we show that very small CdTe nanoparticles continue to grow at high dilution, the growth rate is virtually independent of monomer concentration, nucleation continues after the growth of larger particles has saturated, and the growth rate has a much greater nonlinear dependence on particle size than predicted by theory. We suggest that nanoparticle growth is fast in the liquid phase and then saturates as the particles change phase from liquid to crystal at a threshold size which depends on the growth temperature and not the monomer concentration. The photoluminescence quantum efficiency becomes high when tellurium is depleted in the reaction solution giving a cadmium enriched surface.     

Novel atropoisomeric binaphthyl-containing liquid crystalline copolymers forming chiral nematic phases

Novel liquid crystalline (LC) acrylate side group copolymers, which consist of nematogenic phenyl 4-methoxybenzoate acrylate monomer (A) and novel chiral binaphthyl (BN) methacrylate monomers (MB-n) have been synthesized. The copolymers prepared differ in the spacer lengths of MB-n (n 3,5,11) and in their compositions. The homopolymers of the three new chiral binaphthyl monomers MB-n were also prepared. Copolymers with a low concentration of binaphthyl monomer units (less than 16 mol%) display a cholesteric mesophase. The induced chirality in the polymers is due to atropoisomerism (C2-symmetry) of the molecules. The helical twisting powers (beta), caused by the atropoisomeric units in the synthesized copolymers, were determined, and their temperature dependencies studied. The unusually high negative temperature coefficient of beta observed above the glass transition temperature is explained in terms of conformational changes of the BN molecules in the copolymers.     

Morphology of polymer networks polymerized in highly ordered liquid crystalline phases

The morphology and optical properties of polymer stabilized liquid crystals formed in a more highly ordered low molecular weight liquid crystal solvent were studied. Tetrafunctional, mesogenic monomers (with and without flexible spacers) were polymerized in isotropic, nematic and smectic phases of the LC solvent (4′-octyl-4-cyanobiphenyl) and studied with scanning electron microscopy and cross-polarized light microscopy. The network morphology of the nematic and isotropic phase polymerizations showed strong similarities with the corresponding polymerizations in other solvents. Polymerization in the smectic phase, however, resulted in marked increases in network order and directionality. Most dramatically, even the polymer without flexible spacer formed a fibrous network of rodlike units, in contrast to the random, beaded texture formed by the same polymer in nematic or isotropic conditions. Correspondingly, a large increase in birefringence demonstrated significant polymer orientation and more effective orientational interaction with the liquid crystalline solvent.     

Polymerisation of liquid crystalline phases in binary surfactant/water systems

The self-assembly behaviour of the polymerisable surfactant -undecenyltrimethylammonium bromide (-UTAB) both before and after polymerisation has been investigated. In addition polymerisation of the liquid crystalline phases formed by this surfactant in aqueous solution has been studied. Introduction of the carbon-carbon double bond at the end of the hydrocarbon chain increases the rigidity of the paraffinic chains such that the Krafft curve is shifted to higher temperatures compared with that of dodecyltrimethylammonium bromide, a nonpolymerisable analogue. Both the polymerised and non-polymerised forms have been observed to have the same phase progression, with the polymer being more soluble in water such that the liquid crystalline phases formed at high surfactant concentration are accessible at room temperature. Polymerisation of the liquid crystalline phases of -UTAB indicate that polymerisation proceeds to approximately 40% (in comparison) with 80% in a non-aggregated form) and that the original monomeric matrix is undisturbed upon partial polymerisation.     

Polymerisation of liquid crystalline phases in binary surfactant/water systems

The binary phase behaviour of two potentially polymerisable quaternary ammonium surfactants in water has been investigated. Allyldodecyldimethylammonium bromide (ADAB) a single-chain surfactant displays a conventional phase progression upon increasing concentration. Whereas the doublechain analogue allyldidodecylmethylammonium bromide (ADDAB) forms two lamellar liquid crystalline phases built from surfactant bilayers, which transform via a first order phase transition. The formation of two distinct lamellar phases and their coexistence has been evidenced by optical microscopy, small-angle x-ray scattering and D₂O deuterium quadrupolar nuclear magnetic resonance spectroscopy. The lamellar phase formed at higher surfactant compositions is a normal lamellar phase (typeL ) consisting of bilayers which are on average parallel and flat. The lower compositional lamellar phase (typeL ) in contrast may not be comprised of planar bilayers but rather aggregates having a high degree of curvature in comparison to those of theL phase. The presence of the allyl polymerisable moiety in the head group position of these surfactants has the effect of reducing the rigidity of the surfactant and increasing its solubility in comparison to nonpolymerisable analogues. Polymerisation of the surfactants was attempted by using thermal and photochemical initiation in isotropic and self-assembled systems. Polymerisation occurred to approximately 30% for DADB but did not occur for ADDAB. Where polymerisation did occur the polymer was incorporated into the monomer matrix by interweaving between the surfactant aggregates. The polymers had a molecular wieght not greater than 8000 Daltons, independent of the monomer concentration of the original solution and type of polymerisation.