Effect of molecular structure of a dichroic dye and the ordering of a liquid crystal on the dichroism of the dye-liquid crystal binary mixtures

The orientational ordering of dyes doped into liquid crystals has been investigated. The experimental results show that the ordering of the dyes can be expressed as a function of the order parameter of the liquid crystal host and the molecular structure of the dye. In addition a theory of the ordering of molecules in a binary mixture system has been derived by extending Kimura's theory. The validity of the theory has been confirmed by comparison with the experimental results using various combination of azo dyes and liquid crystals.     

Influence of substituent length in dichroic dye molecules on the orientational properties of guest-host liquid crystal mixtures

The polarized absorption spectra of eight dichroic dyes, alkyl derivatives of 4-amino-(N-ethylnaphthalimide) dissolved in the nematic liquid crystals 5CB and 6CHBT have been measured as a function of temperature. On the basis of these spectra, the guest order parameter has been evaluated. The influence of the alkyl chain length of the dye molecule on the molecular orientation has been examined. Moreover, the nematic-isotropic transition temperatures for the dye-liquid crystal mixtures have been determined. The experimental results have been compared in some detail with calculations made on the basis of the mean field theory for binary mixtures.     

Synthesis and functional properties of green fluorescent poly(methylmethacrylate) for use in liquid crystal systems

The copolymerization of six 4-aminosubstituted-1,8-naphthalimide dyes comprising an allylic polymerizable group with methylmethacrylate has been investigated. The utility of the copolymers prepared as fluorescent component in polymer/liquid crystal systems has been examined. The photophysical and photochemical properties of the systems monomeric dye/liquid crystal and copolymer/liquid crystal have been also discussed. It has been shown that in a liquid crystal mixture 1,8-naphthalimide dyes and respective copolymer/liquid crystals have yellow–green fluorescent color with good photostability. Copyright © 2003 John Wiley & Sons, Ltd.     

Optical components from a new vitrifying liquid crystal

New low molar mass liquid crystalline vitrifying materials have been synthesized and tested for application in optical films. The molecules were based on spiro compounds derived from pentaerythritol and mesogenic groups derived from cyanobiphenylyl moieties. The resulting materials showed glass transition temperatures as high as 85 degrees C and nematic to isotropic phase transition temperatures up to 222 degrees C. Crystallization from the melt was strongly suppressed. Well-aligned, solid, birefringent layers were obtained from the materials by spincoating. Uniaxially oriented layers with an optic axis tilted with respect to the substrate were obtained by spincoating the liquid crystals on pretilt amplification layers. When an anisotropic dye was incorporated in the liquid crystals, polarizers with a tilted absorption axis were obtained. In addition, the compounds were found to be suitable as hosts for photo-induced reorientation of photo-isomerizable dyes.     

Optical components from a new vitrifying liquid crystal

New low molar mass liquid crystalline vitrifying materials have been synthesized and tested for application in optical films. The molecules were based on spiro compounds derived from pentaerythritol and mesogenic groups derived from cyanobiphenylyl moieties. The resulting materials showed glass transition temperatures as high as 85 degrees C and nematic to isotropic phase transition temperatures up to 222 degrees C. Crystallization from the melt was strongly suppressed. Well-aligned, solid, birefringent layers were obtained from the materials by spincoating. Uniaxially oriented layers with an optic axis tilted with respect to the substrate were obtained by spincoating the liquid crystals on pretilt amplification layers. When an anisotropic dye was incorporated in the liquid crystals, polarizers with a tilted absorption axis were obtained. In addition, the compounds were found to be suitable as hosts for photo-induced reorientation of photo-isomerizable dyes.     

Liquid crystal effects on bacterial viability

The primary objective of this research was to test the hypothesis that lyotropic chromonic liquid crystals (neutral grey, red 14, blue 27, cromolyn) are not toxic to bacteria as compared with surfactant-based lyotropic (CPCl and CsPFO) or thermotropic (5CB and E7) liquid crystals. Biocompatibility of most liquid crystals is currently unknown and is required for the development of systems interfacing liquid crystals and biological systems. Potential liquid crystal toxicity was evaluated by two methods. The first examined bacterial survival measured by bacterial growth over 24 hours, after exposure to various liquid crystals. The second toxicity method evaluated liquid crystal effects on bacterial membrane permeability using two fluorescent dyes. Three different types of bacteria were evaluated to assess bacterial structure differences with respect to liquid crystal toxicity. The results of this study indicate that lyotropic chromonic liquid crystals are not toxic to bacteria, whereas thermotropic and surfactant-based lyotropic liquid crystals are toxic to one or more forms of bacteria. We conclude that lyotropic chromonic liquid crystals may be the preferred material in designing liquid crystal-based systems that interact with biological systems, especially in the use of liquid crystal-based biosensors.     

Orientational ordering of liquid crystals containing a difluoro-substituted phenyl ring

The orientational ordering of several liquid crystals containing a difluorosubstituted phenyl ring has been studied through the use of C-13 NMR. The fluorinated phenyl ring of these liquid crystals have C_s symmetry, so three order parameters are required to completely describe the ordering of this ring. All three of these order parameters have been calculated from carbon-fluorine dipolar coupling constants obtained from the carbon-fluorine splittings in the C-13 NMR spectra. Because of the complexity of the fluorine-coupled spectra, variable angle spinning (VAS) was used to resolve the carbon-fluorine splittings. In order to study the orientational ordering over wide ranges of temperature, we have developed an empirical correlation between the order parameter and the value of a carbon-fluorine dipolar coupling constant. This enabled us to study the change in the order parameter with temperature. The results of applying this method to several structurally similar liquid crystals containing the same type of difluorinated phenyl ring are presented. A comparison is made to a similar mono-fluorinated liquid crystal.     

Liquid crystal effects on bacterial viability

The primary objective of this research was to test the hypothesis that lyotropic chromonic liquid crystals (neutral grey, red 14, blue 27, cromolyn) are not toxic to bacteria as compared with surfactant‐based lyotropic (CPCl and CsPFO) or thermotropic (5CB and E7) liquid crystals. Biocompatibility of most liquid crystals is currently unknown and is required for the development of systems interfacing liquid crystals and biological systems. Potential liquid crystal toxicity was evaluated by two methods. The first examined bacterial survival measured by bacterial growth over 24 hours, after exposure to various liquid crystals. The second toxicity method evaluated liquid crystal effects on bacterial membrane permeability using two fluorescent dyes. Three different types of bacteria were evaluated to assess bacterial structure differences with respect to liquid crystal toxicity. The results of this study indicate that lyotropic chromonic liquid crystals are not toxic to bacteria, whereas thermotropic and surfactant‐based lyotropic liquid crystals are toxic to one or more forms of bacteria. We conclude that lyotropic chromonic liquid crystals may be the preferred material in designing liquid crystal‐based systems that interact with biological systems, especially in the use of liquid crystal‐based biosensors.     

Preparation of ZnS nanorods by a liquid crystal template

ZnS nanorods were synthesized in lamellar liquid crystals of C(12)E(4) by mixing zinc ions and thioacetamide (TAA) solution. The effects of the reactant concentration and the surfactant/water molar ratio in the liquid crystal system on the morphology and size of the ZnS particles were investigated. The prepared ZnS particles are regular nanorods having a width of about 60 nm and a length of about 80-380 nm, with a largest aspect ratio of about 6.3. A lamellar liquid crystal templating mechanism has been proposed to interpret the experimental results.     

Proposal of a new method to determine tilt angles of absorption transition moments in host-guest liquid crystal cells

An idea for a method of experimental determination of tilt angles and order parameters of cylindrosymmetric transition moments of liquid crystals and of dyes in host-guest systems is described. Furthermore, first experimental hints are given. With freely rotating molecules, all transition moments result in an isotropic absorbance for UV/VIS-spectroscopy using polarized light. The resulting absorbance becomes anisotropic if the transition moment of the molecules is polarized, the molecules are aligned in a preferential direction, and the free rotation is suppressed. In this case, the measurement of Aiso, Atilt, and Atilt using polarized light is sufficient to calculate the related tilt angle Psi, the order parameter S, and the absorbance A as a function of the polarization angle. The local electric field and its influence on the dichroic ratio of an absorption band has not been considered. The precision of this method is still limited by the photometric accuracy of the spectrometer and the mechanical precision of the goniometric adjustment of the experimental apparatus.     

Crystal-liquid crystal binary phase diagrams

We propose a new theoretical scheme for the binary phase diagrams of crystal-liquid crystal mixtures by a combination of a phase field model of solidification, the Flory-Huggins theory for liquid-liquid mixing and Maier-Saupe-McMillan (FH-MSM) model for nematic and smectic liquid crystal orderings. The phase field theory describes the crystal phase transition of anisotropic organic crystal and/or side chain liquid crystalline polymer crystals while the FH-MSM model explains isotropic, nematic and smectic-A phase transitions. Self-consistent calculations reveal several possible phase diagram topologies of the binary crystal-liquid crystal mixtures. The calculated phase diagrams were found to accord well to the reported experimental results.     

Liquid crystal mediated interactions between nanoparticles in a nematic phase

A continuum theory is used to study the interactions between nanoparticles suspended in nematic liquid crystals. The free energy functional that describes the system is minimized using an Euler-Lagrange approach and an unsymmetric radial basis function method. It is shown that nanoparticle liquid-crystal mediated interactions can be controlled over a large range of magnitudes through changes of the anchoring energy and the particle diameter. The results presented in this work serve to reconcile past discrepancies between theoretical predictions and experimental observations, and suggest intriguing possibilities for directed nanoparticle self-assembly in liquid crystalline media.     

Control of the optical band structure of liquid crystal infiltrated inverse opal by a photoinduced nematic-isotropic phase transition

Recently, photonic band gap (PBG) crystals with lattice parameters comparable to the wavelength of light have attracted much attention, because they offer unique ways in which to control the propagation of light. PBG crystals have applications in laser, quantum optical devices, and so on. For many of these applications, it is important to have the capability of tuning the photonic band structures. The fabrication of such tunable PBG crystals is still a challenge. In this paper, we proposed that switchable PBG crystals could be realized by taking advantage of the phase transition in liquid crystals induced by the photoisomerization of azo dyes. A dynamic change in the optical stop band was demonstrated. Such photoswitchable PBG crystals provide a method by which light can be routed using light.     

Thermotropic biaxial nematic liquid crystals: spontaneous or field stabilized?

An intermediate nematic phase is proposed for the interpretation of recent experimental results on phase biaxiality in bent-core nematic liquid crystals. The phase is macroscopically uniaxial but has microscopic biaxial, and possibly polar, domains. Under the action of an electric field, the phase acquires macroscopic biaxial ordering resulting from the collective alignment of the domains. A phenomenological theory is developed for the molecular order in this phase and for its transitions to purely uniaxial and to spontaneously biaxial nematic phases.     

Nematic ordering and crystal structure of liquid crystals containing a 4-chlorophenyldifluoroethylene unit

Partially fluorinated liquid crystals have many desirable properties such as high impedance and low viscosity. The compounds trans -1-( trans -4-alkylcyclohexyl)-2-(4-chlorophenyl)difluoroethylene have very low viscosities and reasonable nematic ranges, and are very suitable for electro-optic displays. The crystal structure of a compound in this homologous series has been determined by X-ray diffraction. The orientational ordering for this compound and for another homologue in their nematic phases has been studied by the use of one and two dimensional 13C NMR. The proton-decoupled 13C spectra are complex due to splittings from the two F-19 nuclei, but they have been analysed by combining chemical shift anisotropy and variable angle spinning studies. Carbon-proton and carbon-fluorine dipolar coupling constants were obtained, and the order parameters for the two conjugated molecular segments (the chlorophenyl ring and the difluoroethylenic link) were calculated from the dipolar coupling constants. The temperature dependences of the local order parameters of each fragment were studied.     

Influence of dye molecules on the birefringence of liquid crystal mixtures at near infrared frequencies

The optical properties of nematic liquid crystals have been extensively exploited in the production of devices working in the visible range of the spectrum. These same properties can be employed to make devices that function in the near infrared as required for telecommunications applications. However, it is generally observed that the birefringence of liquid crystal mixtures decreases with increasing wavelength, making it important to identify new materials, optimized for use in the near infrared region. One route to high birefringence is to operate close to an absorption band edge, which in the present context implies choosing highly conjugated materials which are potentially colored and, thus, not suited to traditional display applications. In this paper we explore the usefulness of dye molecules as birefringence enhancers in mixtures with conventional nematic liquid crystals. The optical properties, in particular, the absorption edge, polarizability, and birefringence, of families of known dyes are calculated at optical (589 nm) and infrared (1550 nm) wavelengths, using electronic density functional theory. We demonstrate the expected correlation between the proximity of the absorption edge and the magnitude of the birefringence, and estimate the birefringence enhancement occurring when each dye is incorporated in a guest-host system.     

Oligothiophene dyes for guest-host liquid crystal displays

Three types of donor-acceptor-substituted bithiophene and terthiophene compounds were studied as dichroic dyes, which were dissolved in liquid crystals. These compounds were found to have large absorption coefficients, high dichroic ratios, excellent hues, and to be very attractive for guest-host-type liquid crystal displays. They also showed good solvatochromic behaviour in liquid crystal and cyclohexane solutions. These properties were found to be closely related to the solubilities of these compounds in liquid crystals. One donor-acceptorsubstituted bithiophene was found to behave as a polarity indicator in various kinds of liquid crystal.     

Oligothiophene dyes for guest-host liquid crystal displays

Three types of donor-acceptor-substituted bithiophene and terthiophene compounds were studied as dichroic dyes, which were dissolved in liquid crystals. These compounds were found to have large absorption coefficients, high dichroic ratios, excellent hues, and to be very attractive for guest-host-type liquid crystal displays. They also showed good solvatochromic behaviour in liquid crystal and cyclohexane solutions. These properties were found to be closely related to the solubilities of these compounds in liquid crystals. One donor-acceptorsubstituted bithiophene was found to behave as a polarity indicator in various kinds of liquid crystal.     

Alignment of liquid crystal and dichroic dye molecules in mixed Langmuir and Langmuir-Blodgett films

A study of dichroic dye-liquid crystal mixtures (guest-host systems) in monolayers formed at a gas-liquid interface (Langmuir films) and at a solid surface (Langmuir-Blodgett films) has been made. As a host 4- n -octyl-4'-cyanobiphenyl (8CB) or 4- n -pentyl-4"-cyano- p -terphenyl (5CT) were chosen, while three dichroic azo dyes with various molecular structures were used as guest species. The dyes were added to the liquid crystal matrices at a concentration corresponding to the whole range of molar fractions and the surface pressure-mean molecular area isotherms for Langmuir films were recorded. On the basis of the isotherms, conclusions about the molecular organization and the miscibility of the components in the ultrathin films were drawn. The Langmuir films were transferred onto the quartz plates at surface pressures below the collapse point. The polarized absorption spectra of the Langmuir-Blodgett films were recorded and information about the alignment and intermolecular interactions in the mixtures of the non-amphiphilic dichroic dyes and the liquid crystals with strongly polar terminal groups were obtained.