Films solidified from a lyotropic mesophase which retain the cholesteric structure

Solidified cholesteric films of α-helical poly(γ-methyl L -glutamate) and poly(γ-benzyl L -glutamate) were prepared by casting from solutions of the lyotropic cholesteric mesophase. Colored films can be prepared in this manner, so the cholesteric structure is retained with a pitch corresponding to a visible wavelength. Their iridescent colors can cover the full range of the visible spectrum, and the colors remain unchanged for years. Although the films are similar in optical properties to those of fluid cholesteric phases, the temperature dependence of the color is quite different. On stretching, the film undergoes a permanent deformation, and the iridescent color is shifted toward the blue. If t₀ is the initial film thickness and Δt is the change in thickness after stretching the film, the relative change in pitch, ?ΔP/P₀, of the cholesteric structure increases linearly with ?Δt/t₀ in the range ?Δt/t₀ > 0.10. This reduction of the pitch is attributed to a decrease in the number of pseudonematic layers in the span of one pitch, which may be interpreted in terms of delamination using an angle-ply model of the cholesteric structure.     

Intramolecular disorder and its relation to mesophase structure in lyotropic liquid crystals

NMR SPDE measurements are reported for the lamellar (dispersions and multibilayer stacks) and hexagonal phases of sodium octanoate/octanol/D₂O mixtures. In the lamellar L_β and L_γ (gel) phases the octyl chains are rigid and perfectly ordered, while in the lamellar L_α and hexagonal phases they are flexible and disordered. In particular, the measurements show that in the fluid lamellar L_α phase, there is a marked discontinuity in the octyl chain flexibility at the C₅-C₆ segment; this behaviour is identical to that previously reported for the alkyl end-chains in smectic 4,4′-di-n-octyloxyazoxybenzene. In contrast, in the hexagonal phase, there is an effectively continuous flexibility gradient along the whole length of the octyl chain as in nematic 4,4′-di-n-octyloxyazoxybenzene. The behaviour in the lamellar phase is attributed to interference between cooperative conformational modes and localized random thermal fluctuations.     

Refractometry of lyotropic mesophase systems: Ethyl cellulose/m-cresol and ethyl cellulose/acetic acid

An Abbé refractometer with a rotatable polarizer mounted on the eyepiece is used for determining the two principal refractive indices of birefringent concentrated solutions of ethyl cellulose in m-cresol and in acetic acid. At a certain concentration, birefringence appears for both systems, and the concentration agrees with that for the onset of iridescence (here defined as the critical concentration C_a for formation of the liquid-crystalline phase). The birefringence of concentrated solutions depends strongly on concentration and temperature and can be generalized by a master curve. The refractive index increments for both systems are almost independent of temperature at high concentrations.     

The phase diagram of the lyotropic nematic mesophase in the TTAB/NaBr/water system

The phase diagram of the nematic mesophase present in the tetradecyltrimethylammonium bromide/sodium bromide/water ternary system was determined. A calamitic nematic mesophase (N_C) was observed which extends to very high concentrations of electrolyte. The order parameters of the surfactant head group in the mesophases were studied by the NMR quadrupolar splitting of the deuterated surfactant. On increasing the temperature of nematic mesophases with low electrolyte concentrations, a phase separation occurs with the formation of a more highly ordered hexagonal phase and an isotropic phase. Diffusion measurements of the isotropic micellar solution by the NMR PFG method were used to estimate hydrodynamic radii at low surfactant concentrations and to study micelle diffusion as the concentration of the surfactant was increased to the liquid crystalline region. At higher surfactant concentrations, the diffusion coefficient reached a limiting value. The calamitic nematic mesophase in this surfactant/electrolyte/water system appears to be formed by long wormlike micelles.     

Development of mesophase pitch derived mesoporous carbons through a commercially nanosized template

Mesoporous carbons (MCs) with a high surface area (up to 900 m2/g), large pore volume (up to 2.1 cm3/g), high mesopore ratio (94%), and high yield (70%) were successfully prepared from an AR mesophase pitch, using a commercially nanosized silica template. The removal of the template provided some larger mesopores of 25-50 nm (pore I) with a surface area of ca. 300 m2/g, while the successive carbonization opened the closed pores within the carbon body to give smaller mesopores of 2-10 nm (pore II) with a similar surface area. During the carbonization of pitch precursor, the evaporation of volatile components swells the carbon to introduce the second mesopores among the domains and even microdomain units because of their rearrangements and overlappings in the process. The addition of iron salt with the silica template resulted in a remarkable increase of the surface area (ca. 300 m2/g) by introducing mesopores of 3-5 nm. The resultant MCs maintained some graphitizable natures derived from the anisotropic precursor. Their graphitization at 2400 degrees C provided the graphitic structure with large surface areas (270-460 m2/g) and mesoporosity.     

NMR spectra of molecules oriented in a lyotropic mesophase. III—The Spectrum of γ-Hydroxypyridine

Analysis of the ¹H NMR spectrum of γ-hydroxypyridine dissolved in the lyotropic mesophase formed by a 14 : 1 : 1 : 20 mixture (by weight) of sodium dodecyl sulphate, decanol, sodium sulphate and D₂O provides all the spectral parameters with reasonable precision. The chemical shift, the indirect and the direct proton–proton coupling constants are derived. The direct dipolar couplings thus determined are utilised to obtain the relative interproton distances. Information about the molecular orientation and the solvent solute interactions is deduced.     

Origin of lyotropic liquid crystalline mesophase formation and liquid crystalline to mesostructured solid transformation in the metal nitrate salt-surfactant systems

The zinc nitrate salt acts as a solvent in the ZnX-C(12)EO(10) (ZnX is [Zn(H(2)O)(6)](NO(3))(2) and C(12)EO(10) is C(12)H(25)(OCH(2)CH(2))(10)OH) lyotropic liquid crystalline (LLC) mesophase with a drastic dropping on the melting point of ZnX. The salt-surfactant LLC mesophase is stable down to -52 °C and undergoes a phase change into a solid mesostructured salt upon cooling below -52 °C; no phase separation is observed down to -190 °C. The ZnX-C(12)EO(10) mesophase displays a usual phase behavior with an increasing concentration of the solvent (ZnX) in the media with an order of bicontinuous cubic(V(1))-2D hexagonal(H(1))--a mixture of 2D hexagonal and micelle cubic(H(1) + I)-micelle cubic(I)-micelle(L(1)) phases. The phase behaviors, specifically at low temperatures, and the first phase diagram of the ZnX-C(12)EO(10) system was investigated using polarized optical microscopy (POM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), Fourier transform infrared (FTIR), and Raman techniques and conductivity measurements.     

Non-cylindrical symmetry of the ordering matrix of some spectroscopic probes in a lyotropic mesophase studied by 2H N.M.R. spectroscopy

Deuterium N.M.R. spectroscopy has been used to investigate the orientational ordering of perdeuteriated naphthalene and two perdeuteriated fluorescent probes (pyrene and perylene) dissolved in a discotic nematic micellar phase of potassium laurate/potassium chloride/decanol/water. The results show that the ordering tensors of these probes are not cylindrically symmetric.     

1H NMR spectra of benzo[b]furan,benzo[b]thiophene and benzo[b]selenophene oriented in a lyotropic mesophase

The proton nuclear magnetic resonance spectra of benzo[b]-furan, -thiophene and -selenophene oriented in a potassium laurate lyotropic liquid crystal have been analyzed. Geometrical information has been obtained and compared to previous thermotropic results and various hypothetical models.     

Shear-induced orientation of a rigid surfactant mesophase

An optically clear, crystalline, gel-like mesophase is formed by the addition of water to a micellar solution consisting of a mixture of 0.85 M anionic surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and a 0.42 M zwitterionic surfactant phosphatidylcholine (lecithin) in isooctane. At 25 degrees C and water to AOT molar ratio of 70, the system has a columnar hexagonal microstructure with randomly oriented domains. The shear-induced orientation and subsequent relaxation of this structure were investigated by rheological characterization and small-angle neutron scattering (SANS). The rheological response implies that the domains align under shear, and remain aligned for several hours after cessation of shear. Shear-SANS confirms this picture. The sheared gel mesophase retains its alignment as the temperature is increased to 57 degrees C, indicating the potential to conduct templated polymer and polymer-ceramic composite materials synthesis in aligned systems.     

Extreme swelling of a lyotropic lamellar liquid crystal

The evolution of the OBS/water/decane/pentanol lyotropic lamellar crystal is followed from 0% to more than 90% decane content. The lamellar spacing (d) varies then from 35 Å to 11000 Å. The swelling is followed with small angle x-ray scattering and the Bragg divergence in the intensity is found to disappear in moderately swollen lamellar crystal (d from 200 Å up to 800 Å) while the central scattering increases. More striking is the reappearance of the Bragg divergences observed by SAXS (d from 800 Å to 1100 Å) and for extremely swollen lamellar crystals in the angular distribution of scattered light (d from 2 000 Å to 10 000 Å). We discuss these observations along the lines of the recent models of swollen lamellar liquid crystals and in particular the apparent evolution of the dilute lamellae.     

Novel bisindenocarbazole derivative exhibiting a nematic mesophase

In this letter we describe the synthesis of the first liquid crystalline bisindenocarbazole derivative. The novel bisindenocarbazole exhibits a broad nematic mesophase between 180 and 250 °C, which was characterized by polarizing microscopy and small angle X-ray scattering. The material shows an excellent electrochemical stability and a strong blue fluorescence with a quantum yield of 49% in solution.     

High-resolution NMR characterization of a gel-like surfactant mesophase

The addition of phosphatidylcholine to AOT water-in-oil microemulsions leads to the formation of a rigid gel as the water content is increased above a specific threshold. This system is a gel-like crystalline phase where the microstructure evolves from reverse hexagonal to lamellar with increasing water content and/or temperature. Couette sheared (1)H and (31)P NMR experiments carried out at varying temperature and water content show distinct signatures with microstructure evolution. Because the system has been fully characterized through small-angle neutron scattering, it is possible to relate the NMR signatures to the microstructure. The NMR technique therefore complements scattering techniques but is additionally useful because the technique also picks up isotropic signatures from concurrently occurring noncrystalline phases. The use of NMR to identify such lyotropic gel-like crystalline phases allows easy correlation between templated materials synthesis in these phases and phase microstructure. NMR can therefore be used as a probe to understand microstructure in specific surfactant systems and to characterize the retention of microstructure during materials synthesis.     

A new lyotropic liquid crystalline phase formed in hydrocarbon solvents by a deoxyguanosine derivative through extensive hydrogen bonding

Lipophilic deoxyguanosine 1 in pure hydrocarbons or in mixed CHCl3-hydrocarbon solvents forms a new lyotropic liquid crystalline phase characterized by a two dimensional square packing. The structural elements of the phase are ribbon-like assembled species which are completely different from the columnar structures, based on G-quartets, which are the building blocks of the mesophases formed by deoxyguanosine oligonucleotides in water.     

Magnetic nanorods confined in a lamellar lyotropic phase

The dilute lamellar phase of the nonionic surfactant C 12EO 5 was doped with goethite (iron oxide) nanorods up to a fraction of 5 vol %. The interaction between the inclusions and the host phase was studied by polarized optical microscopy (with or without an applied magnetic field) and by small-angle X-ray scattering. We find that, when the orientation of the nanorods is modified using the magnetic field, the texture of the lamellar phase changes accordingly; one can thus induce a homeotropic-planar reorientation transition. On the other hand, the lamellar phase induces an attractive interaction between the nanorods. In more concentrated lamellar phases (under stronger confinement) the particles form aggregates. This behavior is not encountered for a similar system doped with spherical particles, emphasizing the role of particle shape in the interaction between doping particles and the host phase.     

First order transitions to a lyotropic biaxial nematic

The phase diagram of the sodium dodecylsulphate/decanol/water system is studied by²H NMR spectroscopy in the range between the calamitic nematic (N⁺_C) and discotic nematic (N^-_D) phases. In this narrow range a nematic biaxial phase (N_BX) is observed. The phase transitions between the nematic phases are all of first order. The shape of the surfactant aggregates in the nematic phases varies with composition and temperature.     

First order transitions to a lyotropic biaxial nematic

Abstract

The phase diagram of the sodium dodecylsulphate/decanol/water system is studied by²H NMR spectroscopy in the range between the calamitic nematic (N⁺ _C) and discotic nematic (N^? _D) phases. In this narrow range a nematic biaxial phase (N_BX) is observed. The phase transitions between the nematic phases are all of first order. The shape of the surfactant aggregates in the nematic phases varies with composition and temperature.     

Rheology of a miscible polymer blend

Difference spectra of blends of cis-1,4-polyisoprene and atactic poly(vinylethylene), obtained from the measured FTIR spectra of the pure components and the blends, indicate that mixing of these polymers is not accompanied by any specific chemical interactions. Miscibility in this system arises solely due to the small combinatorial entropy of mixing. The conformation and configuration of the polymer chains in the blends are, therefore, identical to those in the pure melts. As a consequence it was found that the entanglement density of the blends varied monotonically with composition. This variation, however, was not in accordance with predictions based simply on the mechanical interaction density. The principle rheological effect of miscible blending was a large change in the monomeric friction coefficient, which arises from the strong dependence of free volume on composition. The zero shear viscosity and the terminal relaxation time of the blends reflected this change in local chain mobility. Empirical relations, which have previously been proposed for the properties of miscible polymer mixtures, were found to be without merit in describing the obtained experimental results.