DNMR measurements of an asymmetric odd liquid crystal dimer: determination of the intramolecular angle and the degree of order of the two rigid cores.

In this work, we present a Deuteron Nuclear Magnetic Resonance (DNMR) study of the non-symmetric odd liquid crystal dimer α-(4-cyanobiphenyl-4'-yloxy)-ω-(1-pyrenimine-benzylidene-4'-oxy) heptane (CBO7O.Py), formed by a pro-mesogenic cyanobiphenyl unit and a bulky pyrene-containing unit, linked via alkoxy flexible chain. We have synthesized two partially deuterated samples: one with the deuterium atoms in the cyanobiphenyl moiety (dCBO7O.Py) and the other one with the deuterium atoms in the pyrenimine-benzylidene unit (CBO7O.dPy). We have performed angular distribution analysis in the SmA glassy state, obtaining the degree of order of both rigid cores and an estimation of the internal molecular angle between both structures. With the results from the angular study, we have been able to determine the degree of order of both rigid units in either the N phase and the SmA phase, far enough from the glass transition. Both rigid cores have the same degree of order close to the nematic-isotropic phase transition, but as the compound is cooled down, the degree of order of the cyanobiphenyl moiety is clearly higher than that of the pyrene-containing unit. The critical behaviour of the order parameter of the pyrene-containing moiety is consistent with the fact that, for CBO7O.Py, the N-I phase transition is tricritical, which seems to indicate that the uniaxial order parameter of the dimer is dominated by the degree of order of the pyrene-containing core.

Comparative dielectric and thermally stimulated-depolarization-current studies of the liquid crystal dimers 1″,9″-bis(4-cyanobiphenyl-4'-yl) nonane and heptane and a binary mixture between them, close to the glass transition.

We have performed dielectric spectroscopy and thermally stimulated-depolarization-current experiments to study the molecular dynamics of the twist-bend nematic phase close to the glass transition of two members of the 1″,7'-bis(4-cyanobiphenyl-4'-yl)alkane homologous series (CBnCB): the liquid crystal (LC) dimers CB9CB and CB7CB, as well as a binary mixture of both. By doping CB9CB with a small quantity of CB7CB, the crystallization is inhibited when cooling the sample down, while the bulk properties of CB9CB are retained and we can investigate the supercooled behavior close to the glass transition. The study reveals that the inter- and intramolecular interactions of the mixture are similar to those of pure CB9CB and confirms that there is a single glass transition in symmetric LC dimers.

Principle of Hot and Cold and Its Clinical Application in Latin American and Caribbean Medicines.

Historically hot and cold theories have been essential for the constitution and practice of Latin American and Caribbean traditional health systems. Nonetheless, the scarcity and dispersion of the available information impedes the recognition of the relevance and intercultural applicability of these medicines, both in the clinical, academic, and political settings. For these reasons, the aim of this narrative review is to describe hot and cold theories in the conformation and clinical practice of Latin American and Caribbean medical systems. Hot and cold classifications apply to the traditional understanding of health, the body, its physiology, and disease, which therapeutic and preventive approaches are based on foods, habits, and medicinal plants of the opposite cold or hot category. There are recognizable similarities between hot and cold theories in Latin American and Caribbean medicines and in other medical cultures. The growing scientific research and evidence contributes to re-signify the clinical applicability of Latin American and Caribbean traditional medicines. Further research about hot and cold theories in Latin American and Caribbean medicines is strongly recommended, to optimize its integration with biomedicine in an equitable intercultural context.

Controllable coherent backscattering of light in disordered media filled with liquid crystal.

We have investigated multiple scattering of light in a disordered system based on liquid crystals for a temperature-controllable random laser. Coherent backscattering measurements at several temperatures have been well fitted by the theoretical model deduced for a random collection of spherical point scatters based on a diffusion approximation. The transport mean free path exclusively depends on the diffusivity of the liquid crystalline phase of the hybrid scattering system. It is shown how the laser threshold excitation intensity is strongly correlated with the transport mean free path.

Cooperative behavior of molecular motions giving rise to two glass transitions in the same supercooled mesophase of a smectogenic liquid crystal dimer.

In the present work, a detailed analysis of the glassy behavior and the relaxation dynamics of the liquid crystal dimer α-(4-cyanobiphenyl-4'-yloxy)-ω-(1-pyrenimine-benzylidene-4'-oxy) heptane (CBO7O.Py) throughout both nematic and smectic-A mesophases by means of broadband dielectric spectroscopy has been performed. CBO7O.Py shows three different dielectric relaxation modes and two glass transition (T_{g}) temperatures: The higher T_{g} is due to the freezing of the molecular motions responsible for the relaxation mode with the lowest frequency (µ_{1L}); the lower T_{g} is due to the motions responsible for the two relaxation modes with highest frequencies (µ_{1H} and µ_{2}), which converge just at their corresponding T_{g}. It is shown how the three modes follow a critical-like description via the dynamic scaling model. The two modes with lowest frequencies (µ_{1L} and µ_{1H}) are cooperative in the whole range of the mesophases, whereas the highest frequency mode (µ_{2}) is cooperative just below some crossover temperature. In terms of fragility, at the glass transition, the ensemble (µ_{1H}+µ_{2}) presents a value of the steepness index and µ_{1L} a different one, meaning that fragility is a property intrinsic to the molecular motion itself. Finally, the steepness index seems to have a universal behavior with temperature for the dielectric relaxation modes of liquid crystal dimers, being almost constant at high temperatures and increasing drastically when cooling the compound down to the glass transition from a temperature about 3/4T_{NI}.

Influence of liquid crystalline phases on the tunability of a random laser.

In this paper, we report the temperature behavior of an optimized disordered photonic system-based liquid crystal by means of heat capacity and refractive index measurements. The scattering system is formed by a porous borosilicate glass random matrix (about 60%) infiltrated with a smectogenic liquid crystal (about 16%) and a small amount of laser dye (0.1%). The rest of the scattering system is about 24% air, giving rise to a high refractive index contrast scattering system. Such a system has the functionality to change the refractive index contrast with temperature due to the liquid crystal temperature behavior. The system, optically pumped by the second harmonic of a Q-switched Nd:YAG pulsed laser working at 532 nm, exhibits random laser action, the threshold of which depends upon the liquid crystalline mesophase. Temperatures of existence of the smectic-B phase correspond to the most optimized random laser. In such a mesophase, the transport mean free path has been determined as about 16 µm in a coherent backscattering experiment.

Understanding the twist-bend nematic phase: the characterisation of 1-(4-cyanobiphenyl-4'-yloxy)-6-(4-cyanobiphenyl-4'-yl)hexane (CB6OCB) and comparison with CB7CB.

The synthesis and characterisation of the nonsymmetric liquid crystal dimer, 1-(4-cyanobiphenyl-4'-yloxy)-6-(4-cyanobiphenyl-4'-yl)hexane (CB6OCB) is reported. An enantiotropic nematic (N)-twist-bend nematic (NTB) phase transition is observed at 109 °C and a nematic-isotropic phase transition at 153 °C. The NTB phase assignment has been confirmed using polarised light microscopy, freeze fracture transmission electron microscopy (FFTEM), (2)H-NMR spectroscopy, and X-ray diffraction. The effective molecular length in both the NTB and N phases indicates a locally intercalated arrangement of the molecules, and the helicoidal pitch length in the NTB phase is estimated to be 8.9 nm. The surface anchoring properties of CB6OCB on a number of aligning layers is reported. A Landau model is applied to describe high-resolution heat capacity measurements in the vicinity of the NTB-N phase transition. Both the theory and heat capacity measurements agree with a very weak first-order phase transition. A complementary extended molecular field theory was found to be in suggestive accord with the (2)H-NMR studies of CB6OCB-d2, and those already known for CB7CB-d4. These include the reduced transition temperature, TNTBN/TNI, the order parameter of the mesogenic arms in the N phase close to the NTB-N transition, and the order parameter with respect to the helix axis which is related to the conical angle for the NTB phase.

Molecular dynamics of a binary mixture of twist-bend nematic liquid crystal dimers studied by dielectric spectroscopy.

We report a comprehensive dielectric characterization of a liquid crystalline binary mixture composed of the symmetric mesogenic dimer CB7CB and the nonsymmetric mesogenic dimer FFO9OCB. In addition to the high-temperature nematic phase, such a binary mixture shows a twist-bend nematic phase at room temperature which readily vitrifies on slow cooling. Changes in the conformational distribution of the dimers are reflected in the dielectric permittivity and successfully analyzed by means of an appropriate theoretical model. It is shown that the dielectric spectra of the mixture reflect the different molecular dipole properties of the components, resembling in the present case the characteristic dielectric spectra of nonsymmetric dimers. Comparison of the nematic and twist-bend nematic phases reveals that molecular dynamics are similar despite the difference in the molecular environment.

Twist, tilt, and orientational order at the nematic to twist-bend nematic phase transition of 1″,9″-bis(4-cyanobiphenyl-4'-yl) nonane: A dielectric, (2)H NMR, and calorimetric study.

The nature of the nematic-nematic phase transition in the liquid crystal dimer 1″,9″-bis(4-cyanobiphenyl-4'-yl) nonane (CB9CB) has been investigated using techniques of calorimetry, dynamic dielectric response measurements, and (2)H NMR spectroscopy. The experimental results for CB9CB show that, like the shorter homologue CB7CB, the studied material exhibits a normal nematic phase, which on cooling undergoes a transition to the twist-bend nematic phase (N(TB)), a uniaxial nematic phase, promoted by the average bent molecular shape, in which the director tilts and precesses describing a conical helix. Modulated differential scanning calorimetry has been used to analyze the nature of the N(TB)-N phase transition, which is found to be weakly first order, but close to tricritical. Additionally broadband dielectric spectroscopy and (2)H magnetic resonance studies have revealed information on the structural characteristics of the recently discovered twist-bend nematic phase. Analysis of the dynamic dielectric response in both nematic phases has provided an estimate of the conical angle of the heliconical structure for the N(TB) phase. Capacitance measurements of the electric-field realignment of the director in initially planar aligned cells have yielded values for the splay and bend elastic constants in the high temperature nematic phase. The bend elastic constant is small and decreases with decreasing temperature as the twist-bend phase is approached. This behavior is expected theoretically and has been observed in materials that form the twist-bend nematic phase. (2)H NMR measurements characterize the chiral helical twist identified in the twist-bend nematic phase and also allow the determination of the temperature dependence of the conical angle and the orientational order parameter with respect to the director.

Dispersion of γ-Alumina Nano-Sized Spherical Particles in a Calamitic Liquid Crystal. Study and Optimization of the Confinement Effects.

We report an experimental study on confined systems formed by butyloxybenzylidene octylaniline liquid crystal (4O.8) + γ-alumina nanoparticles. The effects of the confinement in the thermal and dielectric properties of the liquid crystal under different densities of nanoparticles is analyzed by means of high resolution Modulated Differential Scanning Calorimetry (MDSC) and broadband dielectric spectroscopy. First, a drastic depression of the N-I and SmA-N transition temperatures is observed with confinement, the more concentration of nanoparticles the deeper this depression is, driving the nematic range closer to the room temperature. An interesting experimental law is found for both transition temperatures. Second, the change in shape of the heat capacity peaks is quantified by means of the full width half maximum (FWHM). Third, the confinement does not noticeably affect the molecular dynamics. Finally, the combination of nanoparticles and the external applied electric field tends to favor the alignment of the molecules in metallic cells. All these results indicate that the confinement of liquid crystals by means of γ-alumina nanoparticles could be optimum for liquid crystal-based electrooptic devices.

Distortion-sensitive insight into the pretransitional behavior of 4-n-octyloxy-4'-cyanobiphenyl (8OCB).

Results of studies of the static and dynamic dielectric properties in rod-like 4-n-octyloxy-4'-cyanobiphenyl (8OCB) with isotropic (I)-nematic (N)-smectic A (SmA)-crystal (Cr) mesomorphism, combined with measurements of the low-frequency nonlinear dielectric effect and heat capacity are presented. The analysis is supported by the derivative-based and distortion-sensitive transformation of experimental data. Evidence for the I-N and N-SmA pretransitional anomalies, indicating the influence of tricritical behavior, is shown. It has also been found that neither the N phase nor the SmA phase are uniform and hallmarks of fluid-fluid crossovers can be detected. The dynamics, tested via the evolution of the primary relaxation time, is clearly non-Arrhenius and described via τ(T) = τ(c)(T-T(C))(-φ). In the immediate vicinity of the I-N transition a novel anomaly has been found: Δτ is proportional to 1/(T - T*), where T* is the temperature of the virtual continuous transition and Δτ is the excess over the 'background behavior'. Experimental results are confronted with the comprehensive Landau-de Gennes theory based modeling.

Liquid-crystalline hybrid materials based on [60]fullerene and bent-core structures.

What a core-ker! By the appropriate combination of promesogenic bent-core structures and the C(60)  unit, lamellar polar liquid-crystal phases were induced. The supramolecular organization of the functional fullerene-based assemblies, the temperature range of the soft phase, the stabilization of the mesophase-like order at room temperature, and the molecular switching under an electric field can be tuned, depending on the molecular structure.

Overall monotropic behavior of a metastable phase of biclotymol, 2,2'-methylenebis(4-chloro-3-methyl-isopropylphenol), inferred from experimental and topological construction of the related P-T state diagram.

The melt from the usual monoclinic phase (Phase I) of biclotymol (T(fusI) = 400.5 +/- 1.0 K, Delta(fus)H(I) = 36.6 +/- 0.9 kJ mol(-1)) recrystallizes into another phase, Phase II, that melts at T(fusII) = 373.8 +/- 0.2 K (Delta(fus)H(II) = 28.8 +/- 1.0 kJ mol(-1)). The transformation of Phase II into Phase I is found to be exothermic upon heating either as a direct process at 363 K or through a melting-recrystallization process (II --> liquid --> I). The melting curves, obtained from differential thermal analyses at various pressures ranging from 0 to 85 MPa, diverge as the pressure increases ((dP/dT)(fusI) = 2.54 +/- 0.07 MPa K(-1), (dP/dT)(fusII) = 5.14 +/- 0.85 MPa K(-1)). A topological P-T diagram with no stable phase region for Phase II, and similar to the 4th case of the P-T state diagrams formerly published by Bakhuis Roozeboom, is drawn, thus illustrating the overall monotropic behavior of Phase II.

Re-entrant nematic behavior in the 7OCB+9OCB mixtures: evidence for multiple nematic-smectic tricritical points.

The metastable phase diagram of the two-component system heptyloxycyanobiphenyl (7OCB)+nonyloxycyanobiphenyl (9OCB) was determined by means of modulated differential scanning calorimetry (MDSC) and optical microscopy measurements. It was experimentally established that the 7OCB+9OCB two-component system exhibits a monotropic re-entrant nematic behavior. A complete quantitative thermodynamic analysis, through Oonk's equal G analysis, was performed, allowing for the calculation of the monotropic re-entrant behavior and the prediction of two tricritical points, one of them experimentally accessible for the SmAd-to-N transition and the other non-experimentally accessible for the RN-to-SmAd transition. From specific-heat measurements, latent heats were obtained for those mixtures displaying a first-order SmAd-to-N transition. Additionally, for some mixtures, the specific-heat critical exponents (alpha), through the second-order SmAd-to-N transition, were obtained. Both batches of data enable us to access to the experimental tricritical temperature for the SmAd-to-N transition.

Liquid crystal binary mixtures of 8OCB + 10OCB. Evidence for a smectic A-to-nematic tricritical point.

The two-component system octyloxycyanobiphenyl (8OCB) + decyloxycyanobiphenil (10OCB) has been studied by means of modulated differential scanning calorimetry as well as optical microscopy. The general trends of the phase diagram are similar to the two-component system octylcyanobiphenyl (8CB) + decylcyanobiphenil (10CB), previously published. Evidence for the existence of a TCP have been reported, the molar composition being about 0.33 of 10OCB. Additionally, the smectic mesophase of the 8OCB + 10OCB mixtures has been unmistakably characterized through optical measurements as smectic A for the whole composition range.