Deep eutectic solvents (DESs) are lately expanding their use to more demanding applications upon aqueous dilution thanks to the preservation of the most appealing properties of the original DESs while overcoming some of their most important drawbacks limiting their performance, like viscosity. Both experimental and theoretical works have studied this dilution regime, the so-called “water-in-DES” system, at near-to stoichiometric amounts to the original DES. Herein, we rather studied the high-dilution range of the “water-in-DES” system looking for enhanced performance because of the interesting properties (a further drop of viscosity) and cost (water is cheap) that it offers. In particular, we found that, in the “water-in-DES” system of a ternary DES composed of resorcinol, urea and choline chloride (e.g., RUChClnW, where n represents mol of water per mole of ternary DES), the tetrahedral structure of water was distorted as a consequence of its incorporation, as an additional hydrogen bond donor or hydrogen bond acceptor, into the hydrogen bond complexes formed among the original DES components . DSC confirmed the formation of a new eutectic, with a melting point below that of its respective components, the original ternary DES and water. This depression in the melting point was also observed in the same regime of reline and malicine aqueous dilutions, thus suggesting the universality of this simple procedure (i.e., water addition to reach the high-dilution range of the “water-in-DES” system) to obtain deeper eutectics eventually providing enhanced performances and lower cost.

The two most prominent and ubiquitous features of glasses at low temperatures, namely the presence of tunneling two-level systems and the so-called boson peak in the reduced vibrational density of states, are shown to persist essentially unchanged in highly stabilized glasses, contrary to what was usually envisaged. Specifically, we have measured the specific heat of 110 million-year-old amber samples from El Soplao (Spain), both at very low temperatures and around the glass transition Tg. In particular, the amount of two-level systems, assessed at the lowest temperatures, was surprisingly found to be exactly the same for the pristine hyperaged amber as for the, subsequently, partially and fully rejuvenated samples.

In this work, we review, extend and discuss low-temperature specific-heat experiments, that we have conducted on different molecular (hydrogen-bonded) solids both in crystalline and glassy (either amorphous or orientationally disordered) phases. In particular, we have measured the low-temperature specific heat Cp for a set of simple, well known alcohols: glycerol, propanol and ethanol. For glycerol, we have prepared and measured Cp of both glass and crystal phases down to 0.5 K. The same has been done for propanol, in this case comparing the strikingly different values observed for the two chemical isomers, 1-propanol and 2-propanol. Moreover, ethanol exhibits a very interesting polymorphism presenting three different solid phases at low temperature: a fully ordered (monoclinic) crystal, an orientationally disordered (cubic) crystal or ‘orientational glass’ and the ordinary structural (amorphous) glass. By measuring and comparing the low-temperature specific heat of the three phases, in the boson peak range 2–10 K as well as in the tunnelling-state range below 1 K, we provide a quantitative confirmation that ‘glassy behaviour’, either concerning low-temperature properties or the glass-transition phenomenon itself, is not directly related to the lack of long-range crystalline order occurring in amorphous solids.

Nanocomposite materials obtained by TiO2 incorporation into ethylene–vinyl alcohol copolymers, extensively used in food packaging, are prepared via a straightforward melting process. The structural characteristics of the nanocomposites are examined using wide and small angle X‐ray scattering (WAXS/SAXS), and vibrational infrared and Raman spectroscopies. A microscopy (SEM/TEM) study shows that the materials obtained are highly homogeneous at the nanometric scale, exhibiting an intimate contact between both the organic and inorganic components. TiO2 incorporation into this polymer matrix renders self‐sterilized nanocomposite materials upon light excitation, which are tested against nine micro‐organisms (gram‐positive and gram‐negative bacteria, cocci, and yeasts) typically involved in food contamination and/or degradation. Overall, the nanocomposites display an impressive performance in the killing of all micro‐organisms with a maximum for an oxide content between 2–5 wt %. The measurement of the physico‐chemical properties together with the structural characterization of the materials provide conclusive evidence that the nanocomposites biocidal capability born of the nanometric organo‐inorganic interface and rationalize the existence of a maximum as a function of the TiO2 content.

We investigated through noncommercial calorimetry and elastoacoustic Brillouin experiments the phase diagram of n-butanol and measured the specific heat and the thermal conductivity in a wide low-temperature range for its three different states, namely, glass, crystal, and the so-called "glacial" states. The main aim of the work was to shed light on the controversial issue of these allegedly polyamorphic transitions found in some molecular glass-forming liquids, first reported to occur in triphenyl phosphite and later in n-butanol. Our experimental results show that the obtained glacial state in n-butanol is not a homogenous, amorphous state, but rather a mixture of two different coexisting phases, very likely the (frustrated) crystal phase embedded in a disordered, glassy phase.

We have conducted x-ray diffraction, calorimetric and Brillouin-scattering experiments on n-butanol between 77 and 300 K, aiming to explore the physical nature of the so-called 'glacial state' previously found in n-butanol as well as in triphenyl phosphite. In addition to our structural and thermodynamic studies of the liquid-glass transition and of the stable crystal state in n-butanol, we have found that the metastable 'glacial state' that can be obtained in the temperature range 125-160 K is not a second amorphous state, but rather the result of a frustrated or aborted crystallization process that produces plenty of nanocrystallites embedded in a disordered matrix. The crystalline order of these nanocrystallites of the 'glacial phase' is exactly the same as that well observed in the fully ordered stable crystal into which it transforms by heating above 160 K.

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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 H 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 betweenH NMR and Brillouin spectroscopy when pointing to the DES content where microphase segregation and formation of co-continuous structures occurred.