Electrical Conductivity and Multiple Glassy Dynamics of Crown Ether-Based Columnar Liquid Crystals.

The phase behavior of two unsymmetrical triphenylene crown ether-based columnar liquid crystals bearing different lengths of alkyl chains, KAL465 and KAL468, was investigated using differential scanning calorimetry (DSC). A plastic crystalline (Cry), a columnar liquid crystalline (Colh), and an isotropic phase were observed along with two glass transitions in the Cry phase. The molecular mobility of the KAL compounds was further studied by a combination of broadband dielectric spectroscopy (BDS) and advanced calorimetric techniques. By the BDS investigations, three dielectric active relaxation processes were observed for both samples. At low temperatures, a γ-process in the Cry state was detected and is assigned to the localized fluctuations taking place in the alkyl chains. An α2-process takes place at higher temperatures in the Cry phase. An α3-process was found in the Colh mesophase. The advanced calorimetric techniques consist of fast scanning calorimetry (FSC) and specific heat spectroscopy employing temperature-modulated DSC and FSC. The advanced calorimetric investigations revealed that besides the α2-process in agreement with BDS, there is a second dynamic glass transition (α1-process), which is not observed by dielectric spectroscopy. The results are in good agreement with the glass transitions detected by DSC for this process. The temperature dependences of the relaxation rates of the α1-, α2-, and α3-processes are all different. Therefore, different molecular assignments for the relaxation processes are proposed. In addition to the relaxation processes, a conductivity contribution was explored by BDS for both KAL compounds. The conductivity contribution appears in both Cry and Colh phases, where the conductivity increases by ca. 1 order of magnitude at phase transition from the Cry to the hexagonal phase.

Complex molecular dynamics of a symmetric model discotic liquid crystal revealed by broadband dielectric, thermal and neutron spectroscopy.

The molecular dynamics of the triphenylene-based discotic liquid crystal HAT6 is investigated by broadband dielectric spectroscopy, advanced dynamical calorimetry and neutron scattering. Differential scanning calorimetry in combination with X-ray scattering reveals that HAT6 has a plastic crystalline phase at low temperatures, a hexagonally ordered liquid crystalline phase at higher temperatures and undergoes a clearing transition at even higher temperatures. The dielectric spectra show several relaxation processes: a localized γ-relaxation at lower temperatures and a so called α2-relaxation at higher temperatures. The relaxation rates of the α2-relaxation have a complex temperature dependence and bear similarities to a dynamic glass transition. The relaxation rates estimated by Hyper DSC, Fast Scanning calorimetry and AC Chip calorimetry have a different temperature dependence than the dielectric α2-relaxation and follow the VFT-behavior characteristic for glassy dynamics. Therefore, this process is called α1-relaxation. Its relaxation rates show a similarity with that of polyethylene. For this reason, the α1-relaxation is assigned to the dynamic glass transition of the alkyl chains in the intercolumnar space. Moreover, this process is not observed by dielectric spectroscopy, which supports its assignment. The α2-relaxation is assigned to small scale translatorial and/or small angle fluctuations of the cores. The neutron scattering data reveal two relaxation processes. The process observed at shorter relaxation times is assigned to the methyl group rotation. The second relaxation process at longer time scales agree in the temperature dependence of its relaxation rates with that of the dielectric γ-relaxation.

Self-assembly of liquid crystals in nanoporous solids for adaptive photonic metamaterials.

Nanoporous media exhibit structures significantly smaller than the wavelengths of visible light and can thus act as photonic metamaterials. Their optical functionality is not determined by the properties of the base materials, but rather by tailored, multiscale structures, in terms of precise pore shape, geometry, and orientation. Embedding liquid crystals in pore space provides additional opportunities to control light-matter interactions at the single-pore, meta-atomic scale. Here, we present temperature-dependent 3D reciprocal space mapping using synchrotron-based X-ray diffraction in combination with high-resolution birefringence experiments on disk-like mesogens (HAT6) imbibed in self-ordered arrays of parallel cylindrical pores 17 to 160 nm across in monolithic anodic aluminium oxide (AAO). In agreement with Monte Carlo computer simulations we observe a remarkably rich self-assembly behaviour, unknown from the bulk state. It encompasses transitions between the isotropic liquid state and discotic stacking in linear columns as well as circular concentric ring formation perpendicular and parallel to the pore axis. These textural transitions underpin an optical birefringence functionality, tuneable in magnitude and in sign from positive to negative via pore size, pore surface-grafting and temperature. Our study demonstrates that the advent of large-scale, self-organised nanoporosity in monolithic solids along with confinement-controllable phase behaviour of liquid-crystalline matter at the single-pore scale provides a reliable and accessible tool to design materials with adjustable optical anisotropy, and thus offers versatile pathways to fine-tune polarisation-dependent light propagation speeds in materials. Such a tailorability is at the core of the emerging field of transformative optics, allowing, e.g., adjustable light absorbers and extremely thin metalenses.

Multiple glassy dynamics in dipole functionalized triphenylene-based discotic liquid crystals revealed by broadband dielectric spectroscopy and advanced calorimetry - assessment of the molecular origin.

A selected series of dipole functionalized triphenylene-based discotic liquid crystals (DLCs) was synthesized and investigated in a systematic way to reveal the phase behavior and molecular dynamics. The later point is of particular importance to understand the charge transport in such systems which is the key property for their applications such as organic field-effect transistors, solar cells or as nanowires in molecular electronics, and also to tune the properties of DLCs. The mesomorphic properties were studied by polarizing optical microscopy, X-ray diffraction, and differential scanning calorimetry, which were compared to the corresponding unfunctionalized DLC. The molecular dynamics were investigated by a combination of state-of-the-art broadband dielectric spectroscopy (BDS) and advanced calorimetry such as fast scanning calorimetry (FSC) and specific heat spectroscopy (SHS). Besides localized fluctuations, surprisingly multiple glassy dynamics were detected for all materials for the first time. Glassy dynamics were proven for both processes unambiguously due to the extraordinary broad frequency range covered. The α1-process is attributed to fluctuations of the alky chains in the intercolumnar space because a polyethylene-like glassy dynamics is observed. This corresponds to a glass transition in a confined three-dimensional space. The α2-process found at temperatures lower than α1-process, is assigned to small scale rotational and/or translational in plane fluctuations of the triphenylene core inside distorted columns. This can be considered as a glass transition in a one-dimensional fluid. Therefore, obtained results are of general importance to understand the glass transition, which is an unsolved problem of condensed matter science.

Collective orientational order and phase behavior of a discotic liquid crystal under nanoscale confinement.

The phase behavior and molecular ordering of hexakishexyloxy triphenylene (HAT6) DLCs under cylindrical nanoconfinement are studied utilizing differential scanning calorimetry (DSC) and dielectric spectroscopy (DS), where cylindrical nanoconfinement is established through embedding HAT6 into the nanopores of anodic aluminum oxide (AAO) membranes, and a silica membrane with pore diameters ranging from 161 nm down to 12 nm. Both unmodified and modified pore walls were considered. In the latter case the pore walls of AAO membranes were chemically treated with n-octadecylphosphonic acid (ODPA) resulting in the formation of a 2.2 nm thick layer of grafted alkyl chains. Phase transition enthalpies decrease with decreasing pore size, indicating that a large proportion of the HAT6 molecules within the pores has a disordered structure, which increases with decreasing pore size for both pore walls. In the case of the ODPA-modification, the amount of ordered HAT6 is increased compared to the unmodified case. The pore size dependencies of the phase transition temperatures were approximated using the Gibbs-Thomson equation, where the estimated surface tension is dependent on the molecular ordering of HAT6 molecules within the pores and upon their surface. DS was employed to investigate the molecular ordering of HAT6 within the nanopores. These investigations revealed that with a pore size of around 38 nm, for the samples with the unmodified pore walls, the molecular ordering changes from planar axial to homeotropic radial. However, the planar axial configuration, which is suitable for electronic applications, can be successfully preserved through ODPA-modification for most of the pore sizes.

Quantized Self-Assembly of Discotic Rings in a Liquid Crystal Confined in Nanopores.

Disklike molecules with aromatic cores spontaneously stack up in linear columns with high, one-dimensional charge carrier mobilities along the columnar axes, making them prominent model systems for functional, self-organized matter. We show by high-resolution optical birefringence and synchrotron-based x-ray diffraction that confining a thermotropic discotic liquid crystal in cylindrical nanopores induces a quantized formation of annular layers consisting of concentric circular bent columns, unknown in the bulk state. Starting from the walls this ring self-assembly propagates layer by layer towards the pore center in the supercooled domain of the bulk isotropic-columnar transition and thus allows one to switch on and off reversibly single, nanosized rings through small temperature variations. By establishing a Gibbs free energy phase diagram we trace the phase transition quantization to the discreteness of the layers' excess bend deformation energies in comparison to the thermal energy, even for this near room-temperature system. Monte Carlo simulations yielding spatially resolved nematic order parameters, density maps, and bond-orientational order parameters corroborate the universality and robustness of the confinement-induced columnar ring formation as well as its quantized nature.

Dynamics and ionic conductivity of ionic liquid crystals forming a hexagonal columnar mesophase.

For the first time, the molecular mobility of two linear-shaped tetramethylated guanidinium triflate ionic liquid crystals (ILCs) having different lengths of alkyl chains was investigated using a combination of broadband dielectric spectroscopy (BDS) and specific heat spectroscopy (SHS). By self-assembly, these ILCs can form a hexagonal ordered mesophase besides plastic crystalline phases and the isotropic state. Three dielectric active processes were found using BDS for both samples. At low temperatures, a γ-process in the plastic crystalline state is observed which is assigned to localized fluctuations of methyl groups including nitrogen atoms in the guanidinium head. At higher temperatures but still in the plastic crystalline state, an α1-process takes place. An α2-process was detected using SHS but with a completely different temperature dependence of the relaxation times than that of the α1-relaxation. This result is discussed in detail, and different molecular assignments of the processes are suggested. At even higher temperatures, electrical conductivity is detected and an increase in the DC conductivity by four orders of magnitude at the phase transition from the plastic crystalline to the hexagonal columnar mesophase is found. This result is traced to a change in the charge transport mechanism from a delocalized electron hopping in the stacked aromatic systems (in the plastic phase) to one dominated by an ionic conduction in the quasi-1D ion channels formed along the supermolecular columns in the ILC hexagonal mesophases.

Thermally induced release from polymeric microparticles with liquid core: the mechanism.

Herein we demonstrate how the volatility of a liquid can be manipulated by enclosing microdroplets of the liquid into thin polymeric shells. In this way, composite core-shell microparticles consisting of 80 wt% of a liquid core material and 20 wt% of a polymer can be made 150 °C more stable than the individual core component. The thermal stability of the composite microparticles is found to be determined by the boiling point of the core material and the average particle size, while the role of the particle shell thickness is much less relevant. Two mechanisms responsible for the release of the core material from the microparticles at elevated temperatures were resolved: (1) thermally induced degradation of the shell and (2) diffusion of the core material through the polymeric shell boosted by the increased inner pressure.

Some gastrointestinal tract characteristics of Karayaka ram lambs slaughtered at different weights.

Thirty-one Karayaka ram lambs were slaughtered at different body weights (30 (n = 7), 35 (n = 6), 40 (n = 7), 45 (n = 6), and 50 (n = 5) kg of body weight at fast) to evaluate the growth of their gastrointestinal tract (GIT) characteristics, to determine the relationship among slaughter body weight (SBW) and empty body weight (EBW), whole GIT and segments, and the influence of slaughter weight on the pH of rumen, jejunum, and cecal contents. The effects of the SBW on GIT weight (P < 0.05), stomach (P < 0.001), and intestine (P < 0.05), the body length (P < 0.001) and caecum (P < 0.05), and the relative weights of GIT (P < 0.05), stomach (P < 0.001), and intestine (P < 0.001) were linear whereas that for the length of intestine were quadratic. The effect of SBW were quadratic (P < 0.05) on ratios of stomach to GIT weight and intestine length to intestine weight and rumen pH while, for the intestine to GIT weight ratio (P < 0.001) and caecum pH (P < 0.05), this effect was linear. The results indicated that for all parameters studied, with the exception of intestinal length and cecal pH, linear relationships were observed with SBW indicating steady growth rates for these tissues.