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Liquid-crystalline Phase (liquid-crystalline + phase)
Selected AbstractsMacroscopically Aligned Ionic Self-Assembled Perylene-Surfactant Complexes within a Polymer Matrix,ADVANCED FUNCTIONAL MATERIALS, Issue 13 2008Ari Laiho Abstract Ionic self-assembled (ISA) surfactant complexes present a facile concept for self-assembly of various functional materials. However, no general scheme has been shown to allow their overall alignment beyond local polydomain-like order. Here we demonstrate that ionic complexes forming a columnar liquid-crystalline phase in bulk can be aligned within polymer blends upon shearing, taken that the matrix polymers have sufficiently high molecular weight. We use an ISA complex of N,N,-bis(ethylenetrimethylammonium)perylenediimide/bis(2-ethylhexyl) phosphate (Pery-BEHP) blended with different molecular weight polystyrenes (PS). Based on X-ray scattering studies and transmission electron microscopy the pure Pery-BEHP complex was found to form a two-dimensional oblique columnar phase where the perylene units stack within the columns. Blending the complex with PS lead to high aspect ratio Pery-BEHP aggregates with lateral dimension in the mesoscale, having internal columnar liquid-crystalline order similar to the pure Pery-BEHP complex. When the Pery-BEHP/PS blend was subjected to a shear flow field, the alignment of perylenes can be achieved but requires sufficiently high molecular weight of the polystyrene matrix. The concept also suggests a simple route for macroscopically aligned nanocomposites with conjugated columnar liquid-crystalline functional additives. [source] Formation of Lipid Emulsions and Clear Gels by Liquid Crystal EmulsificationINTERNATIONAL JOURNAL OF COSMETIC SCIENCE, Issue 1 2007T. Suzuki Recently developed emulsion technologies for the formation of fine emulsions, lipid emulsions and clear gels by liquid crystal emulsification were reviewed. As a basic information on liquid crystal emulsification, the structures and characteristic behaviours of lyotropic liquid crystals were summarized. Formation of a liquid crystalline phase was often seen in emulsions and biological systems. The significance of liquid crystal formation during emulsification was analysed by comparing the states and stabilities of emulsions prepared by different processes. Then uses of liquid crystals for formation of the characteristic emulsions and gels were also discussed. In liquid crystal emulsification, an oil phase is dispersed directly into the lamellar liquid-crystalline phase composed of surfactant, glycerol and water to prepare a gel-like oil-in-liquid crystal emulsion. This is followed by dilution with the remaining water to produce an emulsion. From the phase behaviour during emulsification and analysis of the local motion of the liquid crystal membrane by fluorometry, it was confirmed that the interaction between surfactant and a polyol molecule such as glycerol promotes hydrogen bonding and enhances the strength of the lamellar liquid crystal membranes, which results in the formation of oil-in-liquid crystal emulsions. The interaction between the liquid crystal and oil was analysed from the changes in molecular motion of the membrane at the oil-liquid crystal interface using the spin label technique of electron spin resonance (ESR). The fluidity of the liquid crystal membrane did not change when oil was added, and therefore oil-in-liquid crystal emulsions of various oils were prepared by the identical process. This lack of dependence of the liquid crystal membrane on oil results in the unique properties of liquid crystal emulsification, which can be used for oils of various polarity and different molecular constituents. When a self-organizing artificial stratum corneum lipid containing pseudo-ceramide was used as a principal component of the oil, a multilamellar emulsion of concentric lamellar structure was formed. The multilamellar emulsion supplements the physiological function of stratum corneum by the identical mechanism as natural intercellular lipids. High-pressure treatment of the lipid emulsion produced a gel-like emulsion crystal, in which the homogeneous nanoemulsion droplets were arranged in a hexagonal array. This review paper was presented at the Conference of the Asian Societies of Cosmetic Scientists 2005 in Bangkok. [source] Lightly crosslinked, mesomorphic networks obtained through the reaction of dimeric, liquid-crystalline epoxy,imine monomers and heptanedioic acidJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2006David Ribera Abstract We reacted various dimeric, liquid-crystalline epoxy,imine monomers, differing in the length of the central aliphatic spacer or the dipolar moments, with heptanedioic acid. The resulting systems showed a liquid-crystalline phase in some cases, depending on the dimer and on the reaction conditions. The systems were characterized with respect to their mesomorphic properties and then were submitted to dynamic mechanical thermal analysis in both fixed-frequency and frequency-sweep modes in the shear sandwich configuration. The arrangement in the liquid-crystalline phase seemed to be mainly affected both by the polarization of the mesogen and by the reaction temperature, which favored the liquid-crystalline arrangement when it was lying in the range of stability of the dimer mesophase. In agreement with other recent literature data, dynamic mechanical thermal analysis results suggested that the presence of the mesogen directly incorporated into the main chain increased the lifetimes of the elastic modes both in the isotropic phase and in the liquid-crystalline phase with respect to side-chain liquid-crystalline elastomers and that the time,temperature superposition principle did not hold through the liquid-crystalline-to-isotropic transition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44:6270,6286, 2006 [source] Coexistence of Domains with Distinct Order and Polarity in Fluid Bacterial Membranes,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 1 2002Sharon Vanounou ABSTRACT In this study we sought the detection and characterization of bacterial membrane domains. Fluorescence generalized polarization (GP) spectra of laurdan-labeled Escherichia coli and temperature dependencies of both laurdan's GP and fluorescence anisotropy of 1,3-diphenyl-1,3,5-hexatriene (DPH) (rDPH) affirmed that at physiological temperatures, the E. coli membrane is in a liquid-crystalline phase. However, the strong excitation wavelength dependence of rlaurdan at 37°C reflects membrane heterogeneity. Time-resolved fluorescence emission spectra, which display distinct biphasic redshift kinetics, verified the coexistence of two subpopulations of laurdan. In the initial phase, <50 ps, the redshift in the spectral mass center is much faster for laurdan excited at the blue edge (350 nm), whereas at longer time intervals, similar kinetics is observed upon excitation at either blue or red edge (400 nm). Excitation in the blue region selects laurdan molecules presumably located in a lipid domain in which fast intramolecular relaxation and low anisotropy characterize laurdan's emission. In the proteo-lipid domain, laurdan motion and conformation are restricted as exhibited by a slower relaxation rate, higher anisotropy and a lower GP value. Triple-Gaussian decomposition of laurdan emission spectra showed a sharp phase transition in the temperature dependence of individual components when excited in the blue but not in the red region. At least two kinds of domains of distinct polarity and order are suggested to coexist in the liquid-crystalline bacterial membrane: a lipid-enriched and a proteo-lipid domain. In bacteria with chloramphenicol (Cam),inhibited protein synthesis, laurdan showed reduced polarity and restoration of an isoemissive point in the temperature-dependent spectra. These results suggest a decrease in membrane heterogeneity caused by Cam-induced domain dissipation. [source] Conductivity of Oriented Bis-azo Polymer FilmsCHEMPHYSCHEM, Issue 2 2006Dirk Apitz Abstract The conductivity properties of electro-optic, photoaddressable, dense bis-azo chromophore polymer films are investigated by using samples corona poled at various temperatures. A dielectric spectrometer is applied to measure the frequency dependence of the conductivity at different temperatures before and after heating the material to above the glass transition temperature. The results show that the orientation of the chromophores changes the charge-carrier mobility. Ionic conductivity dominates in a more disordered configuration of the material, while the competing process of hole hopping takes over as a transition to a liquid-crystalline phase occurs when the material is heated to much higher than the glass transition temperature. Such microcrystallization strongly enhances the conductivity. [source] Synthesis and Photophysical Studies of a Pyrenylindole and a Phenalenoindole Obtained from Dehydroamino Acid Derivatives , Application as Fluorescent Probes for Biological SystemsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 23 2009Goreti Pereira Abstract Two pyrenyl-dehydroamino acid derivatives were cyclized by a metal-assisted C,N intramolecular cyclization developed in our research group, to give a pyrenylindole and a phenalenoindole. The pyrenylindole was inserted into a peptide by solid-phase coupling, with use of a 2-chlorotrityl chloride resin and a Fmoc strategy. The photophysical properties of the pyrenylindole and phenalenoindole in several solvents were studied and showed that these compounds can be used as fluorescence probes. The results obtained with the peptide labelled with the pyrenylindole moiety show potential for use of this compound as a fluorescence label avoiding the aggregation propensity of pyrene compounds. Photophysical studies of the pyrenylindole and of the phenalenoindole in lipid membranes were also carried out. Steady-state fluorescence anisotropy measurements revealed that both compounds adopt locations inside the lipid bilayers and are able to report the transition between the gel and liquid-crystalline phases. The results point to potential use of these compounds as fluorescent probes for biological systems.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Refractive-index anisotropy and optical dispersion in films of deoxyribonucleic acid,JOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2007Anna Samoc Abstract We have determined the refractive indices in the directions parallel and perpendicular to the surface plane of films of deoxyribonucleic acid (DNA) and their wavelength dispersion. These parameters are fundamental for understanding the properties of waveguiding structures containing DNA-based photonic materials. The orientation of DNA molecules in films and their optical properties are sensitive to the film fabrication and environmental conditions influencing the structure. Prism coupling measurements show ambient-humidity-related changes in the refractive index, birefringence, and anisotropy of the alignment of the DNA molecules in the films studied. These films were 0.5,5 ,m thick, were prepared by both spin coating and casting from aqueous solutions containing 0.1,3 wt % DNA, and were measured in ambient air with relative humidities of 37,58%. The optical properties of the films and the orientation of the DNA molecules are discussed with respect to the mechanism for the formation of the polymer liquid-crystalline phases during film deposition. The dispersion of the refractive indices in films of native DNA has been derived from interference fringes in absorption and reflection spectra in the wavelength range of 350,2700 nm through the fitting of the positions of the fringes with the Sellmeier dispersion formula in combination with the prism coupling data. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 105: 236,245, 2007 [source] Self-Assembly of an Alkylated Guanosine Derivative into Ordered Supramolecular Nanoribbons in Solution and on Solid SurfacesCHEMISTRY - A EUROPEAN JOURNAL, Issue 13 2007Stefano Lena Dr. Abstract We report on the synthesis and self-assembly of a guanosine derivative bearing an alkyloxy side group under different environmental conditions. This derivative was found to spontaneously form ordered supramolecular nanoribbons in which the individual nucleobases are interacting through H-bonds. In toluene and chloroform solutions the formation of gel-like liquid-crystalline phases was observed. Sub-molecularly resolved scanning tunneling microscopic imaging of monolayers physisorbed at the graphite,solution interface revealed highly ordered two-dimensional networks. The recorded intramolecular contrast can be ascribed to the electronic properties of the different moieties composing the molecule, as proven by quantum-chemical calculations. This self-assembly behavior is in excellent agreement with that of 5,- O -acylated guanosines, which are also characterized by a self-assembled motif of guanosines that resembles parallel ribbons. Therefore, for guanosine derivatives (without sterically demanding groups on the guanine base) the formation of supramolecular nanoribbons in solution, in the solid state, and on flat surfaces is universal. This result is truly important in view of the electronic properties of these supramolecular anisotropic architectures and thus for potential applications in the fields of nano- and opto-electronics. [source] Tuning the Polarization Along Linear Polyaromatic Strands for Rationally Inducing Mesomorphism in Lanthanide Nitrate ComplexesCHEMISTRY - A EUROPEAN JOURNAL, Issue 6 2007Emmanuel Terazzi Dr. Abstract The opposite orientation of the ester spacers in the rodlike ligands L,4C12 (benzimidazole-OOC-phenyl) and L,5C12 (benzimidazole-COO-phenyl) drastically changes the electronic structure of the aromatic systems, without affecting their meridional tricoordination to trivalent lanthanides, LnIII, and their thermotropic liquid crystalline (i.e., mesomorphic) behaviors. However, the rich mesomorphism exhibited by the complexes [Ln(L,4C12)(NO3)3] (Ln=La,Lu) vanishes in [Ln(L,5C12)(NO3)3], despite superimposable molecular structures and comparable photophysical properties. Density functional theory (DFT) and time-dependant DFT calculations performed in the gas phase show that the inversion of the ester spacers has considerable effects on the electronic structure and polarization of the aromatic groups along the strands, which control residual intermolecular interactions responsible for the formation of thermotropic liquid-crystalline phases. As a rule of thumb, an alternation of electron-poor and electron-rich aromatic rings favors intermolecular interactions between the rigid cores and consequently mesomorphism, a situation encountered for L,4C12, L,5C12, [Ln(L,4C12)(NO3)3], but not for [Ln(L,5C12)(NO3)3]. The intercalation of an additional electron-rich diphenol ring on going from [Ln(L,5C12)(NO3)3] to [Ln(L,6C12)(NO3)3] restores mesomorphism despite an unfavorable orientation of the ester spacers, in agreement with our simple predictive model. [source] | |||||||||||||