Structure and dynamics of nanoconfined water and aqueous solutions.

This review is devoted to discussing recent progress on the structure, thermodynamic, reactivity, and dynamics of water and aqueous systems confined within different types of nanopores, synthetic and biological. Currently, this is a branch of water science that has attracted enormous attention of researchers from different fields interested to extend the understanding of the anomalous properties of bulk water to the nanoscopic domain. From a fundamental perspective, the interactions of water and solutes with a confining surface dramatically modify the liquid's structure and, consequently, both its thermodynamical and dynamical behaviors, breaking the validity of the classical thermodynamic and phenomenological description of the transport properties of aqueous systems. Additionally, man-made nanopores and porous materials have emerged as promising solutions to challenging problems such as water purification, biosensing, nanofluidic logic and gating, and energy storage and conversion, while aquaporin, ion channels, and nuclear pore complex nanopores regulate many biological functions such as the conduction of water, the generation of action potentials, and the storage of genetic material. In this work, the more recent experimental and molecular simulations advances in this exciting and rapidly evolving field will be reported and critically discussed.

Advances in the study of supercooled water.

In this review, we report recent progress in the field of supercooled water. Due to its uniqueness, water presents numerous anomalies with respect to most simple liquids, showing polyamorphism both in the liquid and in the glassy state. We first describe the thermodynamic scenarios hypothesized for the supercooled region and in particular among them the liquid-liquid critical point scenario that has so far received more experimental evidence. We then review the most recent structural indicators, the two-state model picture of water, and the importance of cooperative effects related to the fact that water is a hydrogen-bonded network liquid. We show throughout the review that water's peculiar properties come into play also when water is in solution, confined, and close to biological molecules. Concerning dynamics, upon mild supercooling water behaves as a fragile glass former following the mode coupling theory, and it turns into a strong glass former upon further cooling. Connections between the slow dynamics and the thermodynamics are discussed. The translational relaxation times of density fluctuations show in fact the fragile-to-strong crossover connected to the thermodynamics arising from the existence of two liquids. When considering also rotations, additional crossovers come to play. Mobility-viscosity decoupling is also discussed in supercooled water and aqueous solutions. Finally, the polyamorphism of glassy water is considered through experimental and simulation results both in bulk and in salty aqueous solutions. Grains and grain boundaries are also discussed.

Structure and dynamics of water confined in cylindrical nanopores with varying hydrophobicity.

We report a detailed study of the main structural and dynamical features of water confined in model Lennard-Jones nanopores with tunable hydrophobicity and finite length ([Formula: see text] Å). The generic model of cylindrical confinement used is able to reproduce the wetting features of a large class of technologically and biologically relevant systems spanning from crystalline nanoporous materials, to mesoporous silica and ion channels. The aim of this work is to discuss the influence of parameters such as wall hydrophobicity, temperature, and pore size on the structural and dynamical features of confined water. Our simulation campaign confirmed the existence of a core domain in which water displays bulk-like structural features even in extreme ([Formula: see text] Å) confinement, while dynamical properties were shown to depend non-trivially on the size and hydrophobicity of the pores. This article is part of the theme issue 'Progress in mesoscale methods for fluid dynamics simulation'.

Effect of trehalose on protein cryoprotection: Insights into the mechanism of slowing down of hydration water.

We study, with molecular dynamics simulations, a lysozyme protein immersed in a water-trehalose solution upon cooling. The aim is to understand the cryoprotectant role played by this disaccharide through the modifications that it induces on the slow dynamics of protein hydration water with its presence. The α-relaxation shows a fragile to strong crossover about 20° higher than that in the bulk water phase and 15° higher than that in lysozyme hydration water without trehalose. The protein hydration water without trehalose was found to show a second slower relaxation exhibiting a strong to strong crossover coupled with the protein dynamical transition. This slower relaxation time importantly appears enormously slowed down in our cryoprotectant solution. On the other hand, this long-relaxation in the presence of trehalose is also connected with a stronger damping of the protein structural fluctuations than that found when the protein is in contact with the pure hydration water. Therefore, this appears to be the mechanism through which trehalose manifests its cryoprotecting function.

Gas-Induced Drying of Nanopores.

Here, we investigate the role of a dilute hydrophobic gas on the phase behavior of water confined in hydrophobic nanopores. Molecular dynamics showed that gas atoms are hydrophobically attracted within the pores, where even a single particle is able to induce spontaneous drying of the whole pore. The drying process is rationalized in terms of its free-energy landscape, revealing that the penetration of a gas atom is able to suppress the drying free-energy barriers of hydrophobic pores. Results provide insights into the role of gases on the wettability of nanopores and evidence of a possibile physical mechanism for the action of volatile anesthetics on some kinds of ion channels. Results also indicate a novel, bioinspired strategy for controlling bubble formation in nanopores for sensing and energy applications.

Protein-Water and Water-Water Long-Time Relaxations in Protein Hydration Water upon Cooling-A Close Look through Density Correlation Functions.

We report results on the translational dynamics of the hydration water of the lysozyme protein upon cooling obtained by means of molecular dynamics simulations. The self van Hove functions and the mean square displacements of hydration water show two different temperature activated relaxation mechanisms, determining two dynamic regimes where transient trapping of the molecules is followed by hopping phenomena to allow to the structural relaxations. The two caging and hopping regimes are different in their nature. The low-temperature hopping regime has a time scale of tenths of nanoseconds and a length scale on the order of 2-3 water shells. This is connected to the nearest-neighbours cage effect and restricted to the supercooling, it is absent at high temperature and it is the mechanism to escape from the cage also present in bulk water. The second hopping regime is active at high temperatures, on the nanoseconds time scale and over distances of nanometers. This regime is connected to water displacements driven by the protein motion and it is observed very clearly at high temperatures and for temperatures higher than the protein dynamical transition. Below this temperature, the suppression of protein fluctuations largely increases the time-scale of the protein-related hopping phenomena at least over 100 ns. These protein-related hopping phenomena permit the detection of translational motions of hydration water molecules longly persistent in the hydration shell of the protein.

Radial distribution functions of water: Models vs experiments.

We study the temperature behavior of the first four peaks of the oxygen-oxygen radial distribution function of water, simulated by the TIP4P/2005, MB-pol, TIP5P, and SPC/E models and compare to experimental X-ray diffraction data, including a new measurement which extends down to 235 K [H. Pathak et al., J. Chem. Phys. 150, 224506 (2019)]. We find the overall best agreement using the MB-pol and TIP4P/2005 models. We observe, upon cooling, a minimum in the position of the second shell simulated with TIP4P/2005 and SPC/E potentials, located close to the temperature of maximum density. We also calculated the two-body entropy and the contributions coming from the first, second, and outer shells to this quantity. We show that, even if the main contribution comes from the first shell, the contribution of the second shell can become important at low temperature. While real water appears to be less ordered at short distance than obtained by any of the potentials, the different water potentials show more or less order compared to the experiments depending on the considered length-scale.

A proposal for the structure of high- and low-density fluctuations in liquid water.

Based on recent experimental data that can be interpreted as indicating the presence of specific structures in liquid water, we build and optimize two structural models which we compare with the available experimental data. To represent the proposed high-density liquid structures, we use a model consisting of chains of water molecules, and for low-density liquid, we investigate fused dodecahedra as templates for tetrahedral fluctuations. The computed infrared spectra of the models are in very good agreement with the extracted experimental spectra for the two components, while the extracted structures from molecular dynamics (MD) simulations give spectra that are intermediate between the experimentally derived spectra. Computed x-ray absorption and emission spectra as well as the O-O radial distribution functions of the proposed structures are not contradicted by experiment. The stability of the proposed dodecahedral template structures is investigated in MD simulations by seeding the starting structure, and remnants found to persist on an ∼30 ps time scale. We discuss the possible significance of such seeds in simulations and whether they can be viable candidates as templates for structural fluctuations below the compressibility minimum of liquid water.

Translational and rotational dynamics of high and low density TIP4P/2005 water.

We use molecular dynamics simulations using TIP4P/2005 to investigate the self- and distinct-van Hove functions for different local environments of water, classified using the local structure index as an order parameter. The orientational dynamics were studied through the calculation of the time-correlation functions of different-order Legendre polynomials in the OH-bond unit vector. We found that the translational and orientational dynamics are slower for molecules in a low-density local environment and correspondingly the mobility is enhanced upon increasing the local density, consistent with some previous works, but opposite to a recent study on the van Hove function. From the analysis of the distinct dynamics, we find that the second and fourth peaks of the radial distribution function, previously identified as low density-like arrangements, show long persistence in time. The analysis of the time-dependent interparticle distance between the central molecule and the first coordination shell shows that particle identity persists longer than distinct van Hove correlations. The motion of two first-nearest-neighbor molecules thus remains coupled even when this correlation function has been completely decayed. With respect to the orientational dynamics, we show that correlation functions of molecules in a low-density environment decay exponentially, while molecules in a local high-density environment exhibit bi-exponential decay, indicating that dynamic heterogeneity of water is associated with the heterogeneity among high-density and between high-density and low-density species. This bi-exponential behavior is associated with the existence of interstitial waters and the collapse of the second coordination sphere in high-density arrangements, but not with H-bond strength.

X-ray Scattering and O-O Pair-Distribution Functions of Amorphous Ices.

The structure factor and oxygen-oxygen pair-distribution functions of amorphous ices at liquid nitrogen temperature ( T = 77 K) have been derived from wide-angle X-ray scattering (WAXS) up to interatomic distances of r = 23 Å, where local structure differences between the amorphous ices can be seen for the entire range. The distances to the first coordination shell for low-, high-, and very-high-density amorphous ice (LDA, HDA, VHDA) were determined to be 2.75, 2.78, and 2.80 Å, respectively, with high accuracy due to measurements up to a large momentum transfer of 23 Å-1. Similarities in pair-distribution functions between LDA and supercooled water at 254.1 K, HDA and liquid water at 365.9 K, and VHDA and high-pressure liquid water were found up to around 8 Å, but beyond that at longer distances, the similarities were lost. In addition, the structure of the high-density amorphous ices was compared to high-pressure crystalline ices IV, IX , and XII, and conclusions were drawn about the local ordering.

Coherent X-rays reveal the influence of cage effects on ultrafast water dynamics.

The dynamics of liquid water feature a variety of time scales, ranging from extremely fast ballistic-like thermal motion, to slower molecular diffusion and hydrogen-bond rearrangements. Here, we utilize coherent X-ray pulses to investigate the sub-100 fs equilibrium dynamics of water from ambient conditions down to supercooled temperatures. This novel approach utilizes the inherent capability of X-ray speckle visibility spectroscopy to measure equilibrium intermolecular dynamics with lengthscale selectivity, by measuring oxygen motion in momentum space. The observed decay of the speckle contrast at the first diffraction peak, which reflects tetrahedral coordination, is attributed to motion on a molecular scale within the first 120 fs. Through comparison with molecular dynamics simulations, we conclude that the slowing down upon cooling from 328 K down to 253 K is not due to simple thermal ballistic-like motion, but that cage effects play an important role even on timescales over 25 fs due to hydrogen-bonding.

Slow-to-fast transition of hydrogen bond dynamics in acetamide hydration shell formation.

The formation of a hydration shell in acetamide aqueous solution has been investigated by means of UV Raman spectroscopy. The experimental results reveal the existence of two distinct regimes of water dynamics. At high acetamide concentration water molecules show a structural and dynamical behavior consistent with the so-called iceberg model. Upon increasing the amount of water we observe the formation of a hydration shell marked by fastening of hydrogen-bond dynamics. Such a behavior may help to shed light on the scientific debate on how water rearranges around the hydrophobic portions of solute molecules (iceberg vs. non-iceberg models).

Thermodynamic hydration shell behavior of glycine.

Glycine aqueous solutions have been studied as a function of temperature and concentration by means of UV Brillouin and Raman spectroscopes. Brillouin spectra provided information on the average relaxation time τα related to the mechanisms of hydrogen bonds (HBs) formation and breaking. The concentration-temperature behavior of τ has been compared to the vibrational dephasing lifetime of atoms involved in HBs, as derived by a lineshape analysis of Raman spectra. We point out how it is possible to trace the thermodynamic behavior of a selected HB from Raman data. In particular, our results confirm the predominant role played in the hydration process by the water molecules surrounding the hydrophobic groups and, furthermore, evidence how at low temperature the HB strength between these molecules is greater than those found in bulk water and between glycine and water molecules.