Microstructure and dynamics in lyotropic liquid crystals. Principles and applications of nuclear spin relaxation

Nuclear spin relaxation of quadrupolar nuclei provides access to a wide range of properties of lyotropic liquid crystals, ranging from the molecular ordering and dynamics at the interface to the macroscopic viscoelastic behaviour. We emphasize here the unique capability of the spin relaxation method to provide detailed geometric and dynamic information relating to the microstructure of lyotropic liquid crystals, i.e. the metric, curvature, and fluctuations of the dividing interface that separates polar and non-polar regions. This information is conveyed to the spin system via the translational diffusion of surfactants or counterions over the interface. The general principles of the spin relaxation method, as applied to lyotropic liquid crystals, are described, with emphasis on the model-independent information content of the relaxation observables and on the relation to microstructure. Specific results for lamellar, hexagonal, cubic, and nematic phases are also described.     

Influence of saddle-splay deformation on lyotropic chromonic liquid crystals confined between two coaxial cylinders

ABSTRACT

A striking feature of lyotropic chromonic liquid crystals confined in cylinder model exhibit double-twist director configurations. Evidence suggests that saddle-splay deformation is among the most important factors for the distortions of director. Previous researches limit the director to distort at a fixed plane (r-? plane) by using specific boundary conditions such as degenerate planar anchoring condition. In this work, we consider lyotropic chromonic liquid crystals confined between two coaxial cylinders with free-surface boundary conditions and Rapini-Papoular-type anchoring conditions. By using finite-difference iterative method to solve the numerical solution of Euler equation, we find that saddle-splay deformation leads to double-twist director configurations under free-surface boundary conditions, which consist of the result under degenerate planar anchoring conditions. Furthermore, at Rapini-Papoular-type anchoring conditions, saddle-splay deformation has a great influence on the director in the radial direction (r direction) and the director distorts in three-dimensional space. Remarkably, our method provides a more accurate theory basis for the measured values of saddle-splay elastic constant K_24。     

Some Emulsion Features

Traditionally, emulsions have been defined as consisting of two liquids, of which one is dispersed in the other as macroscopic drops, stabilized by mono‐molecular layer of surfactant at the interface. However, a large majority of commercial emulsions are more complex than so and the added elements are essential for the properties of the emulsions including their stability.

With this in mind, this treatment of emulsions is divided into emulsions with mono‐layers and multilayers at the interface. In addition, additional elements in emulsions are described; such as lyotropic liquid crystals, vesicles, microemulsion droplets and solid particles, and their potential influence on the emulsion properties is indicated.     

Structural and dielectric behaviour of non-aqueous lyotropic mixtures: influence of amphiphile chain lengths and counter ions

This study highlights the effects of amphiphile chain length and counter ions on the self-assembly and dielectric behaviour of non-aqueous lyotropic liquid crystals. Two-dimensional hexagonal mesophase is seen for short-chain length sodium dodecyl sulphate, while lamellar and multiwall lamellar mesophases are noticed for long-chain length cetyltrimethylammonium bromide and polyoxyethylene (20) sorbitan monolaurate amphiphiles in the non-aqueous domains of ethylene glycol. A strong influence of amphiphile counter ions is seen on static dielectric constant, loss factor, relaxation frequency and relaxation time of these lyotropic mixtures. Refractive indices of these lyotropic phases are also highlighted.     

Narrowing of spontaneous emission and lasing in lyotropic and thermotropic liquid crystals

The narrowing of spontaneous emission and lasing are reported for the first time for a dye-doped lyotropic liquid crystal consisting of a methylbenzylamine solution of polybenzylglutamate (PBLG). Lasing was also studied in twisted nematics based on cholesterol derivatives. PBLG produces a cholesteric liquid crystal (CLC) with selective reflection in the visible region at PBLG concentrations above 55%. A comparison is made of the narrowing of spontaneous emission and lasing in lyotropic vs. thermotropic liquid crystals. In both cases lasing occurs where the selective reflection band overlaps the dye emission band. Thermotropic liquid crystals show a much lower lasing threshold than lyotropic systems. The lasing mechanism and the role of disorder in both systems are discussed.     

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.     

Dielectric relaxation of water molecules in different lyotropic structures of nonylphenoxypoly(ethylenoxy)ethanol (Ark. 9)

Abstract

Dielectric relaxation of water molecules in the lamellar, L_α, cubic and hexagonal, H_α, lyotropic structures of nonylphenoxy-poly(ethylenoxy)ethanol (Ark. 9) has been studied by dielectric time domain spectroscopy in the frequency range between 10 MHz and 10 GHz. The values of the relaxation times, obtained at room temperature, are the following: 41 ps for the L_α phase, 29 ps for the cubic phase and 22 ps for the H_α phase. As is seen, the relaxation time of bound water is distinctly higher than that of pure water, and it depends strongly on the phase structure. The relaxation times measured for the liquid-crystalline phases as well as for pure Ark. 9 obey the Arrhenius law, and the energy barriers obtained have the following values: (20 ± 2) kJ/mol for all the liquid-crystalline phases, and (30 ± 3) kJ/mol for pure Ark. 9. The former is in good agreement with the value found for bound water in lipid systems whereas the latter is characteristic of the isotropic phase of thermotropic liquid crystals.     

Structural,thermal, dielectric and optical behaviour investigations of water-free ZnO/lyotropic liquid crystal nanocolloids

ABSTRACT

Zinc oxide (ZnO) nanoparticles of spherical symmetry (average size of ≈ 20 nm) have been synthesised via a non-aqueous lyotropic liquid crystalline (LLC) templating process. Lyotropic liquid crystalline nanocolloids are prepared via dispersing 0.05, 0.1 and 0.5 wt.% ZnO nanoparticles in non-aqueous lyotropic phase. No structural phase change has been seen with the doping of nanoparticles as stable lamellar phases are observed in all the cases. Stability of the lamellar structure and orientation of the ZnO nanoparticles in the liquid crystalline matrix may be attributed to the interfacial surface charge interactions. A significant increase and pronounced dispersion in dielectric permittivity of the ZnO/LLC nanocolloids could be the result of parallel coupling among guest/host, higher dipole- moment of the ZnO nanoparticles and Maxwell-Wagner polarisation. The variation of relaxation parameters has also been discussed and correlated with the dielectric and structural parameters. ZnO/lyotropic nanocolloids devices exhibit dc conductivity of the order of 10^?5S/m owing to the increase in the number of ions (of the order of 10¹⁹m^?3) in the doped systems. Nanocolloids exhibits, the refractive index of range 1.40 to 1.45 and the wide bandgap of the range 4.1–4.5 eV.     

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.     

The role of non-linear electron spin resonance spectroscopies Perspectives in microscopic studies of liquid-crystalline polymers

Abstract

The advantages and the limits of electron spin resonance applied to the study of microscopic interactions in liquid crystalline polymers are discussed. Difficulties of current E.S.R. techniques in studying the very slow molecular dynamics suggest the search for novel techniques. Two non-linear C.W. E.S.R. techniques are described; multiple irradiation schemes are studied in a unified theoretical treatment. These methods give direct measurements of the longitudinal relaxation dynamics and are completely independent of the inhomogeneous broadening of the spectral lines. Their capabilities for investigating ultra-slow relaxation rates are evidenced.     

ESR studies of the orientational and reorientational properties of mesomorphic polymers

Abstract

The orientational properties of two mesomorphic azobenzene-containing polyacrylates are investigated by ESR spectroscopy using the spin probe technique. Procedures to achieve a uniform alignment of the director in the presence of a static magnetic field are described in detail. The recovery of the alignment after the creation of controlled non-equilibrium states in the presence of a magnetic field is studied. It is found that the recovery time is proportional to the reciprocal square of the static magnetic field, analogous to that which occurs in low molar mass liquid crystals.     

Dimethylmercury in mixtures of thermotropic nematogens

Abstract

The geometry of dimethylmercury was studied in several mixtures of the liquid crystals ZLI 1167 and phase 4. The variation of the geometry is not very large but systematic changes can be detected as a function of the liquid crystal composition. The anisotropics, δ[sgrave], of the ¹H, ¹³C and ¹⁹⁹Hg shielding tensors were investigated by applying two methods based on mixing liquid crystals with opposite diamagnetic anisotropies and by applying various referencing methods. Apart from these, the anisotropy, δJ _HgC, of the ¹⁹⁹Hg–¹³C spin–spin coupling tensor was studied in four mixtures of these liquid crystals, and was found to vary with the solvent.     

Glassy crystalline state and water sorption of alkyl maltosides

A differential scanning calorimetric and sorption calorimetric study of two alkyl maltosides, C8G2 and C10G2, was performed. In the dry state, C8G2 and C10G2 do not form solid crystals but undergo a glass transition upon temperature change. The glass is partly ordered and has the same lamellar structure as the liquid crystals formed by the two maltosides. To reflect the presence of the glass transition and the structure, the terms "glassy crystals" and "glassy liquid crystals" can be used. A mechanism of the relaxation of the glassy crystals based on the results of small-angle X-ray scattering experiments is proposed. Experiments on water sorption showed that the glassy crystals turn into lyotropic liquid crystals upon sorption of water at constant temperature. This isothermal glass transition can be characterized by water content and change of partial molar enthalpy of mixing of water. A method to calculate the phase diagram liquid crystals-glassy liquid crystals is proposed.     

表面活性剂溶致液晶的流变学性质

系统阐述了三种溶致液晶(六角状、立方状和层状液晶)的流变性质,概括了各自的流变性特点并给出了其理论模型,特别对立方相的流变学模型和层状相的剪切诱导转变作用进行了较详细的说明.讨论了因为这种转变而导致的囊泡的形成,并且在表面活性剂和嵌段共聚物中均可观察到剪切诱导的结构转变.     

Modification of the lyotropic liquid crystalline microstructure of amphiphilic block copolymers in the presence of cosolvents

This article reviews the results of recent investigations on the macroscopic (phase behavior) and microscopic (microstructure) aspects of the role of cosolvents on the self-assembly of amphiphilic copolymers. A comprehensive account of the systematic studies performed in ternary isothermal systems consisting of a representative poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) block copolymer (Pluronic P105, EO₃₇PO₅₈EO₃₇), water and a polar cosolvent (such as glycerol, propylene glycol or ethanol) is presented. The effect of cosolvents on the copolymer phase behavior is quantified in terms of the highest cosolvent/water ratio able to maintain the liquid crystalline structures. The effect of cosolvents on the microstructure of the lyotropic liquid crystals is quantified in terms of the degree of relative swelling per cosolvent content per copolymer content, a parameter that characterizes the given cosolvent and copolymer. The set of correlations on the cosolvent effects on the phase behavior or microstructure to the cosolvent physicochemical characteristics (such as octanol/water partition coefficient or solubility parameter) have led to the development of a hypothesis that accounts for the cosolvent effects on the self-assembly of PEO–PPO–PEO block copolymers and can be used to predict them. The rich structural diversity and the potential for a precise and convenient modification of the lyotropic liquid crystalline microstructure of the PEO–PPO–PEO block copolymers is discussed in comparison to the phase behavior of the low-molecular nonionic surfactants.     

Measurement of the rotational viscosity, γ1 of nematic liquid crystals under high pressure

Abstract

A method for the measurement of the rotational viscosity, γ₁ of nematic liquid crystals under high pressure is described. First measurements for the liquid crystals 4'-methoxybenzylidene-4-n-butylaniline, a broad range nematic mixture of substituted cyclohexyl-phenyls and a re-entrant nematic mixture are presented.     

High pressure phase diagrams of two homologous series of Inotropics

Abstract

The hexagonal-isotropic transition is studied in two homologous series of lyotropic liquid crystals. The high pressure phase diagrams are mapped up to 2 kbar for three homologues from each of the Triton X and Triton N series of non-ionic surfactants. We find that an interesting hexagonal-isotropic re-entrant phenomenon is a common feature of the transition lines of homologues in each series. For each homologue in each series, we report a systematic increase in the average value of dP/dT with decreasing concentration correlated with the presence of the re-entrant phenomenon.     

Search for ultra slow molecular motion in liquid crystals by spin thermometry

The existence of a slow dynamic mode, which relaxes the nuclear Zeeman energy at low fields, has been detected in liquid crystals by several nuclear magnetic resonance studies. To data, through, this slow mode has not been uniquely determined. The cross relaxation in the liquid crystal PAA and the dimer-exchange in the alkoxy-benzoic acid homologous series, interfere with the analysis of the low frequency relaxation. In p-(pentyl) phenyl-p-pentyloxy benzoate, which is not a dimer and cross relaxation between protons and other nuclei is not possible, the spin relaxation was analysed at low and high fields. By measuring T₁, T_1ρ, T_1D and applying spin thermometry, the existence of a slow mode was uniquely determined in this liquid crystal.     

Relaxation dispersion and zero-field spectroscopy of thermotropic and lyotropic liquid crystals by fast field-cycling N.M.R.

Abstract

Systematic field-cycling measurements of the T ₁ relaxation dispersion in numerous nematic liquid crystals (azoxybenzenes, Schiff's bases, biphenyls, phenyl-cyclohexanes, cyclo-cyclo-hexanes) confirm our previous observations obtained for PAA and MBBA that order fluctuations of the nematic director are a significant relaxation contribution only at low Lamor frequencies v, i.e. far below the usual megahertz range. Their significance is demonstrated most convincingly by the characteristic square-root dispersion law, T ₁ ～ v ^1/2, which occurs in the kilohertz range and which completely disappears above the nematic–isotropic phase transition. The strength of the collective relaxation mechanism varies by more than two orders of magnitude in the sequence (selection) PAA-d ₈ PAA, PAA-d ₆ PAB, OCB7, MBBA, CB7, PCH7, MBBA-d ₆ MBBA-d ₁₃ and CCH7. This finding can be understood almost quantitatively by the widely differing separations and orientations of proton pairs on the molecules, together with the different viscoelastic parameters of the nematogens. In addition, the underlying slow molecular reorientations have been observed in MBBA and PAA by intensity changes of the zero-field spectra, which are absent for high-field measurements. Similarly, smectic type order fluctuations in layered liquid crystal structures prove to be an effective relaxation mechanism only at low Lamor frequencies. This has been verified by the related linear relaxation dispersion profile, T ₁ ～ v ¹, for both thermotropic systems (TBBA, C₁₂-AA) and lamellar lyotropic mixtures (e.g. potassium laurate in water and phospholipids in water). Our results concerning the time scale of the T ₁ ～ v ^1/2 and T ₁ ~ v ¹ regime do not agree with conclusions drawn from conventional high-field techniques.     

CP/MAS Carbon-13 NMR Study of Spin Relaxation Phenomena of Cellulose Containing Crystalline and Noncrystalline Components

Abstract

Cross-polarization, ¹³C rotating frame spin-lattice relaxation and C laboratory frame spin-lattice relaxation processes have been studied for different cellulose samples by CP/MAS ¹³C NMR spectroscopy. It was found that the CP process can be described by a simple thermodynamic model and relative intensities of the respective resonance lines are consistent with the atomic ratios for the spectra obtained at a contact time of about 1 ms. The observed rotating frame spin-lattice relaxation times T^C ₁₀ were dominantly dependent on the time constant T^D _CH by which ¹³C nuclei were coupled to the ¹H dipolar spin system. It was, therefore, impossible to obtain information about molecular