Translational Diffusion Of Water Research Articles

Water diffusion in complex systems measured by PGSENMR using chemical shift selective stimulated echo: Elimination of magnetization exchange effects.

The interpretation of molecular translational diffusion as measured by pulsed gradient spin-echo NMR (PGSENMR) can be complicated by the presence of chemical exchange and/or dipolar cross-relaxation (including relayed cross-relaxation via spin diffusion). The magnitude of influence depends on the kinetics of exchange and/or dipolar cross-relaxation present within the system as well as the PGSENMR sequences chosen for measurements. First, we present an exchange induced zero-crossing phenomenon for signal attenuation of water in lipidic cubic phases (formed by a mixture of monoolein and water) in the presence of pulsed gradients observed using a standard STimulated Echo (STE) sequence. This magnetization exchange induced zero-crossing phenomenon, a pseudo-negative diffraction-like feature, resembles that reported previously for restricted diffusion when locally anisotropic pores are polydisperse or randomly oriented. We then demonstrate the elimination of these exchange and/or dipolar cross-relaxation induced effects with the use of a chemical shift selective STE (CHESS-STE) sequence, adapted from the previously reported band-selective short transient STE sequence, along with results obtained from the bipolar pulse pair STE sequence for comparison. The CHESS-STE sequence introduced here represents a generic form of PGSENMR sequences for obtaining water diffusion coefficients free from the influence of exchange and/or dipolar cross-relaxation in complex systems. It has potential applications in measuring translational diffusion of water in biopolymer mixtures as well as probing the microscopic structure in materials via water restricted diffusion measured by PGSENMR, particularly when the potential presence of exchange/cross-relaxation is of concern.

Probing Dynamics of Water Mass Transfer in Organic Porous Photocatalyst Water-Splitting Materials by Neutron Spectroscopy.

The quest for efficient and economically accessible cleaner methods to develop sustainable carbon-free energy sources induced a keen interest in the production of hydrogen fuel. This can be achieved via the water-splitting process and by exploiting solar energy. However, the use of adequate photocatalysts is required to reach this goal. Covalent triazine-based frameworks (CTFs) are potential target photocatalysts for water splitting. Both electronic and structural characteristics of CTFs, particularly energy levels, optical band gaps, and porosities are directly relevant to water splitting and can be engineered through chemical design. Porosity can, in principle, be beneficial to water splitting by providing a larger surface area for the catalytic reactions to take place. However, porosity can also affect both charge transport within the photocatalyst and mass transfer of both reactants and products, thus impacting the overall kinetics of the reaction. Here, we focus on the link between chemical design and water (reactant) mass transfer, which plays a key role in the water uptake process and the subsequent hydrogen generation in practice. We use neutron spectroscopy to study the mass transfer of water in two porous CTFs, CTF-CN and CTF-2, that differ in the polarity of their struts. Quasi-elastic neutron scattering is used to quantify the amount of bound water and the translational diffusion of water. Inelastic neutron scattering measurements complement the quasi-elastic neutron scattering study and provide insights into the softness of the CTF structures and the changes in librational degrees of freedom of water in the porous CTFs. We show that two different types of interaction between water and CTFs take place in CTF-CN and CTF-2. CTF-CN exhibits a smaller surface area and lower water uptake due to its softer structure than CTF-2. However, the polar cyano group interacts locally with water leading to a large amount of bound water and a strong rearrangement of the water hydration monolayer, while water diffusion in CTF-2 is principally impacted by microporosity. The current study leads to new insights into the structure-dynamics–property relationship of CTF photocatalysts that pave the road for a better understanding of the guest–host interaction on the basis of water-splitting applications.

Impact of Chemical Structure on the Dynamics of Mass Transfer of Water in Conjugated Microporous Polymers: A Neutron Spectroscopy Study.

Hydrogen fuel can contribute as a masterpiece in conceiving a robust carbon-free economic puzzle if cleaner methods to produce hydrogen become technically efficient and economically viable. Organic photocatalytic materials such as conjugated microporous materials (CMPs) are potential attractive candidates for water splitting as their energy levels and optical band gap as well as porosity are tunable through chemical synthesis. The performances of CMPs depend also on the mass transfer of reactants, intermediates, and products. Here, we study the mass transfer of water (H2O and D2O) and of triethylamine, which is used as a hole scavenger for hydrogen evolution, by means of neutron spectroscopy. We find that the stiffness of the nodes of the CMPs is correlated with an increase in trapped water, reflected by motions too slow to be quantified by quasi-elastic neutron scattering (QENS). Our study highlights that the addition of the polar sulfone group results in additional interactions between water and the CMP, as evidenced by inelastic neutron scattering (INS), leading to changes in the translational diffusion of water, as determined from the QENS measurements. No changes in triethylamine motions could be observed within the CMPs from the present investigations.

Cavity molecular dynamics simulations of liquid water under vibrational ultrastrong coupling.

We simulate vibrational strong coupling (VSC) and vibrational ultrastrong coupling (V-USC) for liquid water with classical molecular dynamics simulations. When the cavity modes are resonantly coupled to the O-H stretch mode of liquid water, the infrared spectrum shows asymmetric Rabi splitting. The lower polariton (LP) may be suppressed or enhanced relative to the upper polariton (UP) depending on the frequency of the cavity mode. Moreover, although the static properties and the translational diffusion of water are not changed under VSC or V-USC, we do find the modification of the orientational autocorrelation function of H2O molecules especially under V-USC, which could play a role in ground-state chemistry.

Interplay between translational diffusion and large-amplitude angular jumps of water molecules.

Understanding the microscopic mechanism of water molecular translational diffusion is a challenging topic in both physics and chemistry. Here, we report an investigation on the interplay between the translational diffusion and the large-amplitude angular jumps of water molecules in bulk water using molecular dynamics simulations. We found that large-amplitude angular jumps are tightly coupled to the translational diffusions. Particularly, we revealed that concurrent rotational jumps of spatially neighboring water molecules induce inter-basin translational jumps, which contributes to the fast component of the water translational diffusion. Consequently, the translational diffusion shows positional heterogeneity; i.e., the neighbors of the water molecules with inter-basin translational jumps have larger probability to diffuse by inter-basin translational jumps. Our control simulations showed that a model water molecule with moderate hydrogen bond strength can diffuse much faster than a simple Lennard-Jones particle in bulk water due to the capability of disturbing the hydrogen bond network of the surrounding water molecules. Our results added to the understanding of the microscopic picture of the water translational diffusion and demonstrated the unique features of water diffusion arising from their hydrogen bond network structure compared with those of the simple liquids.

Brownian Translational Dynamics on a Flexible Surface: Nuclear Spin Relaxation of Fluid Membrane Phases.

A general model for nuclear magnetic resonance (NMR) relaxation studies of fluid bilayer systems is introduced, combining a mesoscopic Brownian dynamics description of the bilayer with atomistic molecular dynamics (MD) simulations. An example is given for dipalmitoylphosphatidylcholine in 2H2O solvent and compared with the experiment. Experimental agreement is within a factor of 2 in the water relaxation rates, based on a postulated model with fixed parameters, which are largely available from the MD simulation. Relaxation rates are particularly sensitive to the translational diffusion of water perturbed by the interface dynamics and structure. Simulation results suggest that a notable deviation in the relaxation rates may follow from the commonly used small-angle approximation of bilayer undulation. The method has the potential to overcome the temporal and spatial limitations in computing NMR relaxation with atomistic MD, as well as the shortcomings of continuum models enabling a consistent description of experiments performed on a solvent lipid and added spin probes. This work opens for possibilities to understand relaxation processes involving systems such as micelles, multilamellar vesicles, red blood cells, and so forth at biologically relevant timescales in great detail.

Mobility of hydrous species in amorphous calcium/magnesium carbonates.

Amorphous calcium carbonate (ACC) is commonly found in many biological materials. As ACC readily crystallizes into calcite, stabilizers, such as anions, cations or macromolecules, often occur to avoid or delay unwanted crystallization. In biogenic ACC, magnesium is commonly present as one of the stabilizing agents. It is generally thought that the presence of mobile water in ACC is responsible for its limited stability and that the strong interaction of Mg2+ with water stabilizes the amorphous structure by retarding dehydration of ACC. To test this hypothesis, we studied the mobility of hydrous species in the model materials ACC, amorphous magnesium carbonate (AMC) and amorphous calcium/magnesium carbonate (ACMC), using quasi elastic neutron scattering (QENS) which is highly sensitive to the dynamics of H atoms. We discovered that hydrous species in the considered amorphous materials consist of water and hydroxide ions, as magnesium ions are incorporated in a ratio of 1 to about 0.6 with OH-. Surprisingly, we found that there is no evidence of translational diffusion of water and hydroxides when calcium is present in the samples, showing that hydrous species are highly static. However, we did observe diffusion of water in AMC with similar dynamics to that found for water in clays. Our results suggest that Mg2+-water interactions alone are not the only reason for the high stability of AMC and ACMC. The stabilizing effect of Mg ions, in addition to Mg-water binding, is likely to be caused by binding to hydroxide in amorphous calcium carbonates. In fact, the incorporation of hydroxides into the amorphous phase results in a mineral composition that is incompatible with any of the known Ca/Mg-carbonate crystal phases, requiring large scale phase separation to reach the composition of even the basic magnesium carbonate minerals artinite and hydromagnesite.

Characteristic features of water dynamics in restricted geometries investigated with quasi-elastic neutron scattering

Understanding the molecular behavior of water in spatially restricted environments is key to better understanding its role in many biological, chemical and geological processes. Here we examine the translational diffusion of water confined to a variety of substrates, from flat surfaces to nanoporous media, in the context of a recently proposed universal scaling law (Chiavazzo 2014) [1]. Using over a dozen previous neutron scattering results, we test the validity of this law, evaluating separately the influence of the hydration amount, and the effects of the size and morphology of the confining medium. Additionally, we investigate the effects of changing instrument resolutions and fitting models on the applicability of this law. Finally, we perform quasi-elastic neutron scattering measurements on water confined inside nanoporous silica to further evaluate this predictive law, in the temperature range 250⩽T⩽290K.

QENS and NMR Study of Water Dynamics in SBA-15 with a Low Water Content

In this study, motions performed by water molecules adsorbed on the silica surface of SBA-15 material with 6.1% of water content (15% of pore filling) were investigated using NMR and Quasielastic Neutron Scattering (QENS) techniques. The results show no sign of translational diffusion of water, but two types of stochastic localized motions were identified, and both described using a model of proton jumps between two sites. For both motions, the characteristic jump distances and correlation times, as well as activation energies, have been extracted and found to differ significantly. On this basis, the faster motion was ascribed to jumps of water molecules between neighboring positions (d = 2.5 A, τ = 4 ps at 300 K, and Ea = 5.2 ± 0.2 kJ/mol from NMR data, and 5.6 ± 1.1 kJ/mol from QENS), while the slower one exhibits a temperature dependent jump distance and was ascribed to jumps of water molecules between more spatially separated positions (d = 2.9–4.3 A, τ = 25 ps at 300 K, and Ea = 16.1 ± 0.3 kJ/mol fro...

Translational diffusion of hydration water correlates with functional motions in folded and intrinsically disordered proteins.

Hydration water is the natural matrix of biological macromolecules and is essential for their activity in cells. The coupling between water and protein dynamics has been intensively studied, yet it remains controversial. Here we combine protein perdeuteration, neutron scattering and molecular dynamics simulations to explore the nature of hydration water motions at temperatures between 200 and 300 K, across the so-called protein dynamical transition, in the intrinsically disordered human protein tau and the globular maltose binding protein. Quasi-elastic broadening is fitted with a model of translating, rotating and immobile water molecules. In both experiment and simulation, the translational component markedly increases at the protein dynamical transition (around 240 K), regardless of whether the protein is intrinsically disordered or folded. Thus, we generalize the notion that the translational diffusion of water molecules on a protein surface promotes the large-amplitude motions of proteins that are required for their biological activity.

Translational diffusion of water inside hydrophobic carbon micropores studied by neutron spectroscopy and molecular dynamics simulation.

When water molecules are confined to nanoscale spacings, such as in the nanometer-size pores of activated carbon fiber (ACF), their freezing point gets suppressed down to very low temperatures (∼150K), leading to a metastable liquid state with remarkable physical properties. We have investigated the ambient pressure diffusive dynamics of water in microporous Kynol ACF-10 (average pore size ∼11.6Å, with primarily slit-like pores) from temperature T=280 K in its stable liquid state down to T=230 K into the metastable supercooled phase. The observed characteristic relaxation times and diffusion coefficients are found to be, respectively, higher and lower than those in bulk water, indicating a slowing down of the water mobility with decreasing temperature. The observed temperature-dependent average relaxation time 〈τ〉 when compared to previous findings indicate that it is the width of the slit pores-not their curvature-that primarily affects the dynamics of water for pore sizes larger than 10 Å. The experimental observations are compared to complementary molecular dynamics simulations of a model system, in which we studied the diffusion of water within the 11.6 Å gap of two parallel graphene sheets. We find generally a reasonable agreement between the observed and calculated relaxation times at the low momentum transfer Q(Q≤0.9Å(-1)). At high Q, however, where localized dynamics becomes relevant, this ideal system does not satisfactorily reproduce the measurements. Consequently, the simulations are compared to the experiments at low Q, where the two can be best reconciled. The best agreement is obtained for the diffusion parameter D associated with the hydrogen-site when a representative stretched exponential function, rather than the standard bimodal exponential model, is used to parametrize the self-correlation function I(Q,t).

Role of Charge Transfer in Water Diffusivity in Aqueous Ionic Solutions.

We performed molecular dynamics simulations on four types of systems containing ion and solvating water. Two systems contained a cation (Na(+) or K(+)), and two other systems an anion (Cl(-) or I(-)). Classical molecular dynamics simulations were performed using three different force fields: a fixed charge force field, a polarizable force field that includes explicit polarization, and also a recently developed force field that includes polarization and charge transfer. These simulations were then compared to first-principles molecular dynamics simulations. While the first-principles simulations showed that the anions accelerated water translational diffusion, the cations slowed it down. In simulations with the classical force fields, only the force field that incorporates explicit charge transfer reproduced this ion-specific behavior. Additional simulations performed to understand the effect of charge transfer demonstrated that two competitive factors determine the behavior of water translational diffusion: the ions diminished charge accelerates water, while the net charge acquired by water either accelerates or slows down its dynamics. Our results show that charge transfer plays a crucial role in governing the water dynamics in aqueous ionic solutions.

Specific Ions Modulate Diffusion Dynamics of Hydration Water on Lipid Membrane Surfaces

Effects of specific ions on the local translational diffusion of water near large hydrophilic lipid vesicle surfaces were measured by Overhauser dynamic nuclear polarization (ODNP). ODNP relies on an unpaired electron spin-containing probe located at molecular or surface sites to report on the dynamics of water protons within ∼10 Å from the spin probe, which give rise to spectral densities for electron–proton cross-relaxation processes in the 10 GHz regime. This pushes nuclear magnetic resonance relaxometry to more than an order of magnitude higher frequencies than conventionally feasible, permitting the measurement of water moving with picosecond to subnanosecond correlation times. Diffusion of water within ∼10 Å of, i.e., up to ∼3 water layers around the spin probes located on hydrophilic lipid vesicle surfaces is ∼5 times retarded compared to the bulk water translational diffusion. This directly reflects on the activation barrier for surface water diffusion, i.e., how tightly water is bound to the hydrophilic surface and surrounding waters. We find this value to be modulated by the presence of specific ions in solution, with its order following the known Hofmeister series. While a molecular description of how ions affect the hydration structure at the hydrophilic surface remains to be answered, the finding that Hofmeister ions directly modulate the surface water diffusivity implies that the strength of the hydrogen bond network of surface hydration water is directly modulated on hydrophilic surfaces.

Water scaffolding in collagen: Implications on protein dynamics as revealed by solid‐state NMR

Solid-state NMR studies of collagen samples of various origins confirm that the amplitude of collagen backbone and sidechain motions increases significantly on increasing the water content. This conclusion is supported by the changes observed in three different NMR observables: (i) the linewidth dependence on the 1H decoupling frequency; (ii) 13C CSA changes for the peptide carbonyl groups, and (iii) dephasing rates of 1H-13C dipolar couplings. In particular, a nearly threefold increase in motional amplitudes of the backbone librations about C-Cα or N-Cα bonds was found on increasing the added water content up to 47 wt%D2 O. On the basis of the frequencies of NMR observables involved, the timescale of the protein motions dependent on the added water content is estimated to be of the order of microseconds. This estimate agrees with that from wideline T2(1)H NMR measurements. Also, our wideline 1H NMR measurements revealed that the timescale of the microsecond motions in proteins reduces significantly on increasing the added water content, i.e., an ∼15-fold increase in protein motional frequencies is observed on increasing the added water content to 45 wt% D2 O. The observed changes in collagen dynamics is attributed to the increase in water translational diffusion on increasing the amount of added water, which leads to more frequent "bound water/free water" exchange on the protein surface, accompanied by the breakage and formation of new hydrogen bonds with polar functionalities of protein.

Water Conduction through a Peptide Nanotube

When inserted into lipid bilayers, synthetic channels formed by cyclic peptides of alternated d- and l-α-amino acids have been shown to modulate the permeability of the cell wall, thereby endowing them with potential bactericidal capability. Details of the underlying energetics of the permeation events remain, however, only fragmentary. Water conduction in a peptide nanotube formed by eight cyclo-(LW)4 subunits embedded in a fully hydrated palmitoyloleylphosphatidylcholine bilayer has been investigated using molecular-dynamics simulations with a time-dependent bias. The topology of the reconstructed free-energy landscape delineating the transport of water mirrors the arrangement of the cyclic peptides in the open-ended tubular structure. Within the nanotube, the small, periodic free-energy barriers, on the order of kBT, arising between adjacent peptide subunits, are suggestive of unhampered translocation. It still remains that translational diffusion of water in the hollow cylindrical cavity is necessarily affected by its interaction with the accessible polar moieties of the constituent d- and l-α-amino acids. By combining diffusivity measurements with the free-energy landscape, we put forth a reaction-rate theory to describe the conduction kinetics of water inside the peptide nanotube.

Influence of Ions on Water Diffusion—A Neutron Scattering Study

Using quasielastic neutron scattering spectroscopy, we measured the averaged translational diffusion of water in solutions of biologically relevant salts, NaCl, a kosmotrope, and KCl, a chaotrope. The analysis revealed the striking difference in the influence of these ions on water dynamics. While the averaged water diffusion slows down in the presence of the structure making (kosmotrope) Na(+) ion, the diffusion becomes faster in the presence of the structure breaking (chaotrope) K(+) ion. The latter means that, despite strong Coulombic interactions introduced by the K(+) ions, their disruption of the hydrogen-bonding network is so significant that it leads to faster diffusion of the water molecules.

Self-Assembly of Gemini Surfactants: A Computer Simulation Study

The self-assembly behavior of gemini (dimeric or twin-tail) dicarboxylate disodium surfactants is studied using molecular dynamics simulations. A united atom model is employed for the surfactants with fully atomistic counterions and water. This gemini architecture, in which two single tailed surfactants are joined through a flexible hydrophobic linker, has been shown to exhibit concentration-dependent aqueous self-assembly into lyotropic phases including hexagonal, gyroid, and lamellar morphologies. Our simulations reproduce the experimentally observed phases at similar amphiphile concentrations in water, including the unusual ability of these surfactants to form gyroid phases over unprecedentedly large amphiphile concentration windows. We demonstrate quantitative agreement between the predicted and experimentally observed domain spacings of these nanostructured materials. Through careful conformation analyses of the surfactant molecules, we show that the gyroid phase is electrostatically stabilized related to the lamellar phase. By starting with a lamellar phase, we show that use of a bulkier N(CH(3))(4)(+) counterion in place of Na(+) drives the formation of a gyroid phase. Decreasing the charge on the surfactant headgroups by carboxylate protonation decreases the degree of order in the lamellar phase. Using our models, we show that the translational diffusion of water and the Na(+) counterions is decreased by several orders of magnitude over the studied concentration range, and we attribute these effects to strong correlations between the mobile species and the surfactant headgroups.

Impact of Pore Size and Pore Surface Composition on the Dynamics of Confined Water in Highly Ordered Porous Silica

The impact of pore size and pore surface composition on water dynamics confined in highly ordered porous silica material (MCM-41) was investigated using neutron scattering for correlation times in the picosecond range. Samples were synthesized by the hydrothermal route and grafted via the hydrolytic surface sol–gel method to obtain pore wall surfaces with Si–OH, Al–OH, or Zr–OH terminations and pore sizes from 2 to 2.7 nm. The samples were characterized after grafting using nitrogen adsorption–desorption isotherms and small-angle X-ray scattering. At room temperature, the analysis of the quasi-elastic neutron scattering data shows a decrease of mean square displacement of the mobile protons with the pore size and when Si–OH surface termination is replaced by Al–OH and Zr–OH. The water translational diffusion coefficients are close to the bulk value whatever the samples. The amounts of fixed protons depend on the pore size and the ability of the grafted layers to immobilize the water molecules which were determined also from thermogravimetric and differential thermal analysis. This last result highlights that pore surface composition could be the predominant parameter affecting the fixed proton content at this time scale.

Molecular Simulation Study of Water Mobility in Aerosol-OT Reverse Micelles

In this work, we present results from molecular dynamics simulations on the single-molecule relaxation of water within reverse micelles (RMs) of different sizes formed by the surfactant aerosol-OT (AOT, sodium bis(2-ethylhexyl)sulfosuccinate) in isooctane. Results are presented for RM water content w(0) = [H(2)O]/[AOT] in the range from 2.0 to 7.5. We show that translational diffusion of water within the RM can, to a good approximation, be decoupled from the translation of the RM through the isooctane solvent. Water translational mobility within the RM is restricted by the water pool dimensions, and thus, the water mean-squared displacements (MSDs) level off in time. Comparison with models of diffusion in confined geometries shows that a version of the Gaussian confinement model with a biexponential decay of correlations provides a good fit to the MSDs, while a model of free diffusion within a sphere agrees less well with simulation results. We find that the local diffusivity is considerably reduced in the interfacial region, especially as w(0) decreases. Molecular orientational relaxation is monitored by examining the behavior of OH and dipole vectors. For both vectors, orientational relaxation slows down close to the interface and as w(0) decreases. For the OH vector, reorientation is strongly affected by the presence of charged species at the RM interface and these effects are especially pronounced for water molecules hydrogen-bonded to surfactant sites that serve as hydrogen-bond acceptors. For the dipole vector, orientational relaxation near the interface slows down more than that for the OH vector due mainly to the influence of ion-dipole interactions with the sodium counterions. We investigate water OH and dipole reorientation mechanisms by studying the w(0) and interfacial shell dependence of orientational time correlations for different Legendre polynomial orders.

Impact of chemical treatments on the behavior of water in Nafion® NRE-212 by 1H NMR: Self-diffusion measurements and proton quantization

In this article, we have studied by 1H NMR the behavior of water in Nafion under acid, sodium and potassium forms which arises from different chemical treatments with or without EDTA. Self-diffusion coefficients were measured by PGSTE (Pulsed Gradient STimulated Echo) whereas integration of the proton spectrum provides a quantitative information about water content. Examination of the self-diffusion coefficients of water in Nafion shows clearly that: (i) in the acid form, the use of a chelating agent does not affect translational diffusion of water, (ii) regardless of sample conditioning, water within Nafion in acid form diffuses more rapidly than in sodium and potassium forms, in particular at low water content (at λ=3.4, D=5.4×10−7cm2s−1 vs. 7.2×10−8cm2s−1), and (iii) for a given water amount, water diffusion is identical in sodium and potassium forms. Point (ii) is due to the presence of oxonium ions within Nafion in acid form, favoring both vehicle and Grotthuss mechanisms. It is also due to a higher number of protons available for diffusion (we find an average value of 1.19 in acid form vs. 0.91 in sodium form). Our results suggest in the case of Nafion in acid form that, at low water content, diffusion occurs by jumps between different sites. Moreover, plotting self-diffusion coefficients vs. relative humidity leads to a clear differentiation between sodium and potassium cations, related to their respective solvation number.