Dynamics of water in partially crystallized solutions of glass forming materials and polymers: Implications on the behavior of bulk water

There is no simpler compound than water. It is the most copious substance on Earth and the most important constituent for life, as we know. There is also a continuous scientific interest due to its exceptional and infrequent properties, such as a density maximum at 4 ℃ (at atmospheric pressure), a high specific heat capacity, and a low viscosity under high pressure, among other macroscopic properties. The origin of the unusual properties of water is evidenced at lower temperatures in the no man’s land temperature region (235–150 K), where bulk water cannot remain in an amorphous state. Instead, in this region, bulk water crystallizes in a complex phase diagram with more than 16 crystalline phases. Therefore, most of the work done so far on supercooled water focuses on the investigation of the dynamics when crystallization is suppressed using different types of confinements, such as nano-cavities or by mixing water with other solutes (polymers, proteins, or DNA). On the contrary, in this chapter, we will use broadband dielectric spectroscopy to analyze the dynamics of aqueous solutions and confined water when it is partially crystallized, i.e., when liquid water and ice coexist. With this technique, it is possible to obtain information about the molecular relaxations in both amorphous and crystalline phases. We have analyzed the results of this semi-crystalline water and compared them with the response of supercooled water in fully amorphous solutions. Finally, we discuss the implications of these results on the behavior of bulk water.The authors gratefully acknowledge CSIC (i-LINK + program LINKB 20012), Spanish Ministerio de Ciencia, Innovacion y Universidades code: PID2019-104650GB-C21 (MCIU/AEI/FEDER, UE) and the Swedish Research Council (grant no. 2015-05434).Peer reviewe

Dynamics of hydration water in gelatin and hyaluronic acid hydrogels

[EN] We employed broadband dielectric spectroscopy (BDS), for the investigation of the water dynamics in partially hydrated hyaluronic acid (HA), and gelatin (Gel), enzymatically crosslinked hydrogels, in the water fraction ranges [Formula: see text]. Our results indicate that at low hydrations ([Formula: see text]), where the dielectric response of the hydrogels is identical during cooling and heating, water plasticizes strongly the polymeric matrix and is organized in clusters giving rise to [Formula: see text]-process, secondary water relaxation and to an additional slower relaxation process. This later process has been found to be related with the dc charge conductivity and can be described in terms of the conduction current relaxation mechanism. At slightly higher hydrations, however, always below the hydration level where ice is formed during cooling, we have recorded in HA hydrogel a strong water dielectric relaxation process, [Formula: see text], which has Arrhenius-like temperature dependence and large time scale resembling relaxation processes recorded in bulk low density amorphous solid water structures. This relaxation process shows a strong-to-fragile transition at [Formula: see text]C and our data suggest that the VTF-like process recorded at [Formula: see text]C is controlled by the same molecular process like long range charge transport. In addition, our data imply that the crossover temperature is related with the onset of structural rearrangements (increase in configurational entropy) of the macromolecules. In partially crystallized hydrogels ([Formula: see text]) HA exhibits at low temperatures the ice dielectric process consistent with the bulk hexagonal ice, whereas Gel hydrogel exhibits as main low temperature process a slow relaxation process that refers to open tetrahedral structures of water similar to low density amorphous ice structures and to bulk cubic ice. Regarding the water secondary relaxation processes, we have shown that the [Formula: see text]-process and the [Formula: see text] process are activated in water hydrogen bond networks with different structures.The support from Ministerio de Economia, Industria y Competitividad (MINECO) through the MAT2016-76039-C4-1-R project (including the FEDER funds) is acknowledged. The CIBER-BBN initiative is funded by the VI National R&D&I Plan 2008-2011, Iniciativa Ingenio 2010, Consolider Program. CIBER actions are financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund. 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