Persistent Local Structural Defectiveness as an Early Time Predictor of Intermittent Glassy Relaxation Events in Supercooled Water.

To become a glass from the metastable supercooled state, a liquid experiences a dramatic dynamical slowing down within a narrow temperature window. However, the attainment of solid rigidity is not the result of breaking translational symmetry as in a crystal: the structure of the resulting amorphous solid strikingly resembles that of the liquid state. Moreover, the supercooled liquid is dynamically heterogeneous; that is, the dynamics varies by orders of magnitude from one region of the sample to another, but the establishment of the existence of strong structural differences between such regions has demanded hard efforts along the years. In this work, we focus precisely on such a structure-dynamics link for supercooled water showing that local regions with structural defectiveness are persistent during the structural relaxation of the system, hence acting as early time predictors of later intermittent glassy relaxation events.

Correlations between defect propensity and dynamical heterogeneities in supercooled water.

A salient feature of supercooled liquids consists in the dramatic dynamical slowdown they undergo as temperature decreases while no significant structural change is evident. These systems also present dynamical heterogeneities (DH): certain molecules, spatially arranged in clusters, relax various orders of magnitude faster than the others. However, again, no static quantity (such as structural or energetic measures) shows strong direct correlations with such fast-moving molecules. In turn, the dynamic propensity approach, an indirect measure that quantifies the tendency of the molecules to move in a given structural configuration, has revealed that dynamical constraints, indeed, originate from the initial structure. Nevertheless, this approach is not able to elicit which structural quantity is, in fact, responsible for such a behavior. In an effort to remove dynamics from its definition in favor of a static quantity, an energy-based propensity has also been developed for supercooled water, but it could only find positive correlations between the lowest-energy and the least-mobile molecules, while no correlations could be found for those more relevant mobile molecules involved in the DH clusters responsible for the system's structural relaxation. Thus, in this work, we shall define a defect propensity measure based on a recently introduced structural index that accurately characterizes water structural defects. We shall show that this defect propensity measure provides positive correlations with dynamic propensity, being also able to account for the fast-moving molecules responsible for the structural relaxation. Moreover, time dependent correlations will show that defect propensity represents an appropriate early-time predictor of the long-time dynamical heterogeneity.

Biophysical interactions of phenolic acids from yerba mate tea with lipid membranes.

Yerba mate (Ilex paraguariensis) tea is a well know source of phenolic antioxidants compounds. Caffeoyl derivatives are the primary constituents that account for the antioxidant capacity of this beverage. It was proposed that the interaction of polyphenols with lipid bilayers of various cell types provides the molecular rationale for their hallmark antioxidant and anti-inflammatory activities. In this study, atomistic molecular dynamics (MD) simulations were carried out in order to outline a detailed picture of the molecular interactions between three caffeoyl acids derivatives and two different lipid bilayers. We show that the three phenolic acids are able to interact at the upper regions of lipid bilayers, confining their action to the membrane surface; moreover, the strength of these interactions relay on the probability of metabolite protonation once inserted in the bilayer.

Structural aspects of an energy-based water classification index and the structure-dynamics link in glassy relaxation.

An energy-based structural indicator for water, [Formula: see text], has been recently introduced by our group. In turn, in this work we aim at: (1) demonstrating that [Formula: see text] is indeed able to correctly classify water molecules between locally structured tetrahedral (T) and locally distorted (D) ones, circumventing the usual problem of certain previous indicators of overestimating the distorted state; (2) correlating [Formula: see text] with dynamic propensity, a measure of the molecular mobility tendency, in order to seek for the existence of a connection between structure and dynamics within the supercooled regime. More specifically, in the first part of this work we will show that [Formula: see text] accurately discriminates between merely thermally deformed local molecular arrangements and truly distorted molecules (defects). This fact will be made evident not only from radial distribution function results but also from the dynamic propensity distributions of the different kinds of molecules. In turn, we shall devote the second part of this work to finding correlations between T and D molecules with low- and high-dynamic-propensity molecules, respectively, thus revealing the existence of a link between local structure and dynamics, while also making evident the dominant role of the D molecules (defects) in the structural relaxation. Moreover, the availability of a proper molecular classification technique will enable us to study the timescale of such influence of structure on dynamics by defining a modified dynamic propensity measure and by applying it to the structured and unstructured water molecular states.

Structural features of high-local-density water molecules: Insights from structure indicators based on the translational order between the first two molecular shells.

The two-liquids scenario for liquid water assumes the existence of two competing preferential local molecular structural states characterized by either low or high local density. While the former is expected to present good local order thus involving privileged structures, the latter is usually regarded as conforming a high-entropy unstructured state. A main difference in the local arrangement of such "classes" of water molecules can be inferred from the degree of translational order between the first and second molecular shells. This is so, since the low-local-density molecules present a clear gap between the first two shells while in the case of the high-local-density ones, one or more molecules from the second shell have collapsed toward the first one, thus populating the intershell region. Some structural indicators, like the widely employed local structure index and the recently introduced ζ index, have been devised precisely on the basis of this observation, being successful in detecting well-structured low-local-density molecules. However, the nature of the high-local-density state has been mainly disregarded over the years. In this work we employ molecular dynamics simulations for two water models (the extended simple point charge model and the five-site model) at the liquid and supercooled regimes combined with the inherent dynamics approach (energy minimizations of the instantaneous configurations) in order to both rationalize the detailed structural and topological information that these indicators provide and to advance in our understanding of the high-density state.

Comparing the performance of two structural indicators for different water models while seeking for connections between structure and dynamics in the glassy regime.

In this work, we compare the performance of two structural indicators based on the degree of translational order up to the second coordination shell in three water models: SPC/E, TIP4P/2005, and TIP5P. Beyond directly contrasting their distributions for different temperatures to evidence their usefulness in estimating the fraction of structured and unstructured molecules and, when possible, their classification capability, we also correlate them with an indirect measure of structural constraint: the dynamic propensity. Furthermore, this procedure enables us to show the existence of evident correlations between structural and dynamical information. More specifically, we find that locally structured molecules display a preference for low dynamic propensity values and, more conspicuously, that locally unstructured molecules are extremely subject to high dynamic propensity. This result is particularly relevant for the supercooled regime where the establishment of firm links between the structure and dynamics has remained rather elusive since the occurrence of dynamics that vary in orders of magnitude upon supercooling usually contrast with barely noticeable overall structural changes.

Water populations in restricted environments of lipid membrane interphases.

We employ molecular dynamics simulations to study the hydration properties of Dipalmitoylphosphatidylcholine (DPPC) bilayers, both in the gel and the liquid crystalline states. We show that while the tight hydration centers (PO and CO moieties) are significantly hydrated in both phases, the gel-fluid transition involves significant changes at the second hydration shell, particularly at the buried region between the hydrocarbon tails. Thus, while almost no buried water population exists in the gel state below the carbonyls, this hydrophobic region becomes partially water accesible in the liquid crystalline state. We shall also show that such water molecules present a lower H-bond coordination as compared to the molecules at the primary hydration shell. This means that, while the latter are arranged in relatively compact nanoclusters (as already proposed), the buried water molecules tend to organize themselves in less compact structures, typically strings or branched strings, with a scarce population of isolated molecules. This behavior is similar to that observed in other hydration contexts, like water penetrating carbon nanotubes or model hydrophobic channels or pores, and reflects the reluctance of water to sacrifice HB coordination.

Hydration and Nanoconfined Water: Insights from Computer Simulations.

The comprehension of the structure and behavior of water at interfaces and under nanoconfinement represents an issue of major concern in several central research areas like hydration, reaction dynamics and biology. From one side, water is known to play a dominant role in the structuring, the dynamics and the functionality of biological molecules, governing main processes like protein folding, protein binding and biological function. In turn, the same principles that rule biological organization at the molecular level are also operative for materials science processes that take place within a water environment, being responsible for the self-assembly of molecular structures to create synthetic supramolecular nanometrically-sized materials. Thus, the understanding of the principles of water hydration, including the development of a theory of hydrophobicity at the nanoscale, is imperative both from a fundamental and an applied standpoint. In this work we present some molecular dynamics studies of the structure and dynamics of water at different interfaces or confinement conditions, ranging from simple model hydrophobic interfaces with different geometrical constraints (in order to single out curvature effects), to self-assembled monolayers, proteins and phospholipid membranes. The tendency of the water molecules to sacrifice the lowest hydrogen bond (HB) coordination as possible at extended interfaces is revealed. This fact makes the first hydration layers to be highly oriented, in some situations even resembling the structure of hexagonal ice. A similar trend to maximize the number of HBs is shown to hold in cavity filling, with small subnanometric hydrophobic cavities remaining empty while larger cavities display an alternation of filled and dry states with a significant inner HB network. We also study interfaces with complex chemical and geometrical nature in order to determine how different conditions affect the local hydration properties. Thus, we show some results for protein hydration and, particularly, some preliminary studies on membrane hydration. Finally, calculations of a local hydrophobicity measure of relevance for binding and self-assembly are also presented. We then conclude with a few words of further emphasis on the relevance of this kind of knowledge to biology and to the design of new materials by highlighting the context-dependent and non-additive nature of different non-covalent interactions in an aqueous nanoenvironment, an issue that is usually greatly overlooked.