Deep eutectic solvents (DESs) offer a suitable alternative to conventional solvents in terms of both performance and cost-effectiveness. Some DESs also offer certain green features, the greenness of which is notoriously enhanced when combined with water. Aqueous DES dilutions are therefore attracting great attention as a novel green medium for biotechnological processes, with the aqueous dilutions of reline - a DES composed of urea and choline chloride - being one of the most studied systems. Despite their macroscopic homogeneous appearance, both 1H NMR spectroscopic studies and molecular dynamics simulations have revealed the occurrence of certain dynamic heterogeneity at a microscopic molecular level. Ultrasonic measurements were also used with the aim of getting further insights but nonconclusive results were obtained. Herein, we have studied aqueous reline dilutions by Brillouin spectroscopy given its proved suitability for detecting local structure rearrangements in liquid mixtures of H-bonded co-solvents. Brillouin spectroscopy revealed the formation of a co-continuous structure resulting from local structure rearrangements and micro-segregation into aqueous and DES phases. Interestingly, there is agreement between 1H NMR and Brillouin spectroscopy when pointing to the DES content where microphase segregation and formation of co-continuous structures occurred.

Reline aqueous solutions behaving as liquid mixtures of H-bonded co-solvents: microphase segregation and formation of co-continuous structures as indicated by Brillouin and 1H NMR spectroscopies

Nanophase separation in aqueous dilutions of a ternary DES as revealed by Brillouin and NMR spectroscopy

The nature of the glassy state and of the glass transition of structural glasses is still a matter of debate This debate stems predominantly from the kinetic features of the thermal glass transition However the glass transition has at least two faces: the kinetic one which becomes apparent in the regime of low relaxation frequencies and a static one observed in static or frequency-clamped linear and non-linear susceptibilities New results concerning the so-called α-relaxation process show that the historical view of an unavoidable cross-over of this relaxation time with the experimental time scale is probably wrong and support instead the existence of an intrinsic glass transition In order to prove this, three different experimental strategies have been applied: studying the glass transition at extremely long time scales, the investigation of properties which are not sensitive to the kinetics of the glass transition and studying glass transitions which do not depend at all on a forced external time scale

About the Nature of the Structural Glass Transition: An Experimental Approach

Controlling thermoelastic anisotropy of liquid crystals (LCs) is important for achieving reliable structural stability and efficient heat dissipation, especially for high-performance LC devices. A solid understanding of the thermoelastic anisotropy and its relation with the LC molecular structure is, however, still missing. Here, we studied the direction-dependent mechanical and thermal properties of 5-n-octyl-2-(4-n-octyloxy-phenyl)-pyrimidine (PYP8O8) in a wide temperature range, covering five phases (i.e., crystalline, smectic C, smectic A, nematic, and liquid), by Brillouin light spectroscopy and temperature wave analysis, respectively. We found that the mechanical anisotropy is much smaller than the thermal anisotropy at LC phases; both anisotropies show strong phase dependence, with the biggest change occurring at the crystalline to LC phase transition; and the anisotropy of the phonon mean-free path correlates with the structural anisotropy of the rigid core of the LC molecule. The analysis of the temperature-dependent thermoelastic anisotropy of LCs yields insights into structure-based phonon engineering.

https://pubs.acs.org/doi/pdf/10.1021/acs.jpcc.9b04270

Temperature-Dependent Thermoelastic Anisotropy of the Phenyl Pyrimidine Liquid Crystal.

Brillouin spectroscopy, dilatometry and calorimetry results have been used to investigate the temperature anomaly of the mode and thermal Gruneisen parameters around the glass transition of the fragile liquid poly(vinyl acetate). These results are compared with those of the strong liquids and 4-cyano-4-6-alkylbiphenyl.

https://iopscience.iop.org/article/10.1088/0953-8984/8/50/012/pdf

Anharmonic properties of fragile and strong liquids: temperature dependence of the mode Grüneisen parameter

Within this work we present Brillouin and ultrasonic investigations performed on the liquid crystals p-methoxybenzylidene p-(n-butylaniline) (MBBA), p-azoxyanisol (PAA), 4-cyano-4-n-alkylbiphenyles (nCB), and 4-n-pentoxybenzylidene-4'-n-octoaniline (5O.8). Special attention has been paid to the evolution of a significant splitting of the two longitudinal polarized acoustic modes within the nematic phase. Angle-resolving Brillouin spectroscopy allowed the determination of the complete stiffness tensors and hence a discussion of the propagation of quasitransverse polarized acoustic modes in the nematic state of liquid crystals. We analyze the behavior of the eigenvectors of the relevant acoustic modes and discuss their significance for the propagation of quasishear modes. For 5O.8 we report an acoustic instability within its nematic state. We confirm the existence of a universal thermal relaxation mechanism of weak activation energy for the nematic state of classical liquid crystals. The observed hypersonic anisotropy is discussed in terms of that relaxation mechanism and is compared with that of glass-forming liquid crystals.

D. Rogez

Papers

Second-order elasticity of liquid crystals within their nematic state at high frequencies

Universal relaxation behavior of classical liquid crystals at hypersonic frequencies