Bulk Water Diffusion Research Articles

Dynamical properties of solid and hydrated collagen: Insight from nuclear magnetic resonance relaxometry.

1H spin-lattice Nuclear Magnetic Resonance relaxometry experiments have been performed for collagen and collagen-based artificial tissues in the frequency range of 10 kHz-20MHz. The studies were performed for non-hydrated and hydrated materials. The relaxation data have been interpreted as including relaxation contributions originating from 1H-1H and 1H-14N dipole-dipole interactions, the latter leading to Quadrupole Relaxation Enhancement effects. The 1H-1H relaxation contributions have been decomposed into terms associated with dynamical processes on different time scales. A comparison of the parameters for the non-hydrated and hydrated systems has shown that hydration leads to a decrease in the dipolar relaxation constants without significantly affecting the dynamical processes. In the next step, the relaxation data for the hydrated systems were interpreted in terms of a model assuming two-dimensional translational diffusion of water molecules in the vicinity of the macromolecular surfaces and a sub-diffusive motion leading to a power law of the frequency dependencies of the relaxation rates. It was found that the water diffusion process is slowed down by at least two orders of magnitude compared to bulk water diffusion. The frequency dependencies of the relaxation rates in hydrated tissues and hydrated collagen are characterized by different power laws (ωH-β, where ωH denotes the 1H resonance frequency): the first of about 0.4 and the second close to unity.

The influence of temperature on cellulose swelling at constant water density

We have in this paper investigated how water sorbs to cellulose. We found that both cellulose nanofibril (CNF) and cellulose nanocrystal (CNC) films swell similarly, as they are both mainly composed of cellulose. CNF/CNC films subjected to water at 0.018 kg/m3 at 25 °C and 39 °C, showed a decrease in swelling from ~ 8 to 2%. This deswelling increased the tensile index of CNF-films by ~ 13%. By molecular modeling of fibril swelling, we found that water sorbed to cellulose exhibits a decreased diffusion constant compared to bulk water. We quantified this change and showed that diffusion of sorbed water displays less dependency on swelling temperature compared to bulk water diffusion. To our knowledge, this has not previously been demonstrated by molecular modeling. The difference between bulk water diffusion (DWW) and diffusion of water sorbed to cellulose (DCC) increased from DWW − DCC ~ 3 × 10–5 cm/s2 at 25 °C to DWW − DCC ~ 8.3 × 10–5 cm/s2 at 100 °C. Moreover, water molecules spent less successive time sorbed to a fibril at higher temperatures.

A new insight into the adsorption behavior of NPAM on kaolinite/water interface: Experimental and theoretical approach

The adsorption behavior and bridging mechanism of NPAM and kaolinite in aqueous solution were investigated using MD simulation and experiment. Turbidity, Zeta potential, and floc size were involved in the analysis of the settlement test; microscopic interaction mechanisms were further discovered via interaction energy, number and water density distribution, and self-diffusion coefficient. It emerged that too little NPAM has a high diffusivity in bulk water, NPAM cannot be directly adsorbed to kaolinite surfaces and the bridging mechanism is difficult to appear; experiment results in the high turbidity of the supernatant and inability to form flocs. As the number of chains increases, the adsorption probability and the adsorption capacity of NPAM on kaolinite surfaces are improved, the range of NPAM diffusion in bulk water expands and the bridging performance is enhanced; the turbidity decreases and the floc formation. When the number of NPAM chains is excessive, the interaction energy of NPAM in surface water with kaolinite surfaces is slightly weakened, NPAM in bulk water may weaken the combined affinity, but the bridging effect is further enhanced; which increases the turbidity and floc size. The adsorption of NPAM in surface water and kaolinite surfaces is the prerequisite for the formation of bridging mechanism, NPAM in bulk water is the crux to enhancing bridging performance. A large number of water molecules and NPAM have strong competitive adsorption on kaolinite surfaces. The interaction energy between NPAM and kaolinite surfaces in aqueous solution is mainly contributed by van der Waals interaction.

Effect of Modification on the Fluid Diffusion Coefficient in Silica Nanochannels.

The diffusion behavior of fluid water in nanochannels with hydroxylation of silica gel and silanization of different modified chain lengths was simulated by the equilibrium molecular dynamics method. The diffusion coefficient of fluid water was calculated by the Einstein method and the Green–Kubo method, so as to analyze the change rule between the modification degree of nanochannels and the diffusion coefficient of fluid water. The results showed that the diffusion coefficient of fluid water increased with the length of the modified chain. The average diffusion coefficient of fluid water in the hydroxylated nanochannels was 8.01% of the bulk water diffusion coefficient, and the diffusion coefficients of fluid water in the –(CH2)3CH3, –(CH2)7CH3, and –(CH2)11CH3 nanochannels were 44.10%, 49.72%, and 53.80% of the diffusion coefficients of bulk water, respectively. In the above four wall characteristic models, the diffusion coefficients in the z direction were smaller than those in the other directions. However, with an increase in the silylation degree, the increased self-diffusion coefficient due to the surface effect could basically offset the decreased self-diffusion coefficient owing to the scale effect. In the four nanochannels, when the local diffusion coefficient of fluid water was in the range of 8 Å close to the wall, Dz was greater than Dxy, and beyond the range of 8 Å of the wall, the Dz was smaller than Dxy.

Atomic-scale ion transistor with ultrahigh diffusivity.

Biological ion channels rapidly and selectively gate ion transport through atomic-scale filters to maintain vital life functions. We report an atomic-scale ion transistor exhibiting ultrafast and highly selective ion transport controlled by electrical gating in graphene channels around 3 angstroms in height, made from a single flake of reduced graphene oxide. The ion diffusion coefficient reaches two orders of magnitude higher than the coefficient in bulk water. Atomic-scale ion transport shows a threshold behavior due to the critical energy barrier for hydrated ion insertion. Our in situ optical measurements suggest that ultrafast ion transport likely originates from highly dense packing of ions and their concerted movement inside the graphene channels.

Gated ion flow in graphene oxide membranes

Nanofluidics Cells are adept at fast, gated ion flow through tailored channels, which is key to many biological processes. Xue et al. developed ion transistors from reduced graphene oxide membranes and observed a field-enhanced diffusivity of the ions (see the Perspective by Hinds). By applying electrical gating, the average surface potential on the graphene layer could be controlled, thus altering the energy barrier for ion intercalation into the channel and leading to very high diffusion rates. The authors observed selective ion transport two orders of magnitude faster than the ion diffusion in bulk water. Science , this issue p. [501][1]; see also p. [459][2] [1]: /lookup/doi/10.1126/science.abb5144 [2]: /lookup/doi/10.1126/science.abh2618

Mechanism of Water Dynamics in Hyaluronic Dermal Fillers Revealed by Nuclear Magnetic Resonance Relaxometry.

1H spin−lattice nuclear magnetic resonance relaxation experiments were performed for five kinds of dermal fillers based on hyaluronic acid. The relaxation data were collected over a broad frequency range between 4 kHz and 40 MHz, at body temperature. Thanks to the frequency range encompassing four orders of magnitude, the dynamics of water confined in the polymeric matrix was revealed. It is demonstrated that translation diffusion of the confined water molecules exhibits a two‐dimensional character and the diffusion process is slower than diffusion in bulk water by 3–4 orders of magnitude. As far as rotational dynamics of the confined water is concerned, it is shown that in all cases there is a water pool characterized by a rotational correlation time of about 4×10−9 s. In some of the dermal fillers a fraction of the confined water (about 10 %) forms a pool that exhibits considerably slower (by an order of magnitude) rotational dynamics. In addition, the water binding capacity of the dermal fillers was quantitatively compared.

Classical Molecular Dynamics with Mobile Protons.

An important limitation of standard classical molecular dynamics simulations is the inability to make or break chemical bonds. This restricts severely our ability to study processes that involve even the simplest of chemical reactions, the transfer of a proton. Existing approaches for allowing proton transfer in the context of classical mechanics are rather cumbersome and have not achieved widespread use and routine status. Here we reconsider the combination of molecular dynamics with periodic stochastic proton hops. To ensure computational efficiency, we propose a non-Boltzmann acceptance criterion that is heuristically adjusted to maintain the correct or desirable thermodynamic equilibria between different protonation states and proton transfer rates. Parameters are proposed for hydronium, Asp, Glu, and His. The algorithm is implemented in the program CHARMM and tested on proton diffusion in bulk water and carbon nanotubes and on proton conductance in the gramicidin A channel. Using hopping parameters determined from proton diffusion in bulk water, the model reproduces the enhanced proton diffusivity in carbon nanotubes and gives a reasonable estimate of the proton conductance in gramicidin A.

Nuclear-magnetic-resonance relaxation due to the translational diffusion of fluid confined to quasi-two-dimensional pores.

Nuclear-magnetic-resonance (NMR) relaxation experimentation is an effective technique for nondestructively probing the dynamics of proton-bearing fluids in porous media. The frequency-dependent relaxation rate T_{1}^{-1} can yield a wealth of information on the fluid dynamics within the pore provided data can be fit to a suitable spin diffusion model. A spin diffusion model yields the dipolar correlation function G(t) describing the relative translational motion of pairs of ^{1}H spins which then can be Fourier transformed to yield T_{1}^{-1}. G(t) for spins confined to a quasi-two-dimensional (Q2D) pore of thickness h is determined using theoretical and Monte Carlo techniques. G(t) shows a transition from three- to two-dimensional motion with the transition time proportional to h^{2}. T_{1}^{-1} is found to be independent of frequency over the range 0.01-100 MHz provided h≳5 nm and increases with decreasing frequency and decreasing h for pores of thickness h<3 nm. T_{1}^{-1} increases linearly with the bulk water diffusion correlation time τ_{b} allowing a simple and direct estimate of the bulk water diffusion coefficient from the high-frequency limit of T_{1}^{-1} dispersion measurements in systems where the influence of paramagnetic impurities is negligible. Monte Carlo simulations of hydrated Q2D pores are executed for a range of surface-to-bulk desorption rates for a thin pore. G(t) is found to decorrelate when spins move from the surface to the bulk, display three-dimensional properties at intermediate times, and finally show a bulk-mediated surface diffusion (Lévy) mechanism at longer times. The results may be used to interpret NMR relaxation rates in hydrated porous systems in which the paramagnetic impurity density is negligible.

Divide-and-Conquer-Type Density-Functional Tight-Binding Simulations of Hydroxide Ion Diffusion in Bulk Water.

The diffusion of the hydroxide ion in bulk water was examined by linear-scaling divide-and-conquer density-functional tight-binding molecular dynamics (DC-DFTB-MD) simulations using three different-sized unit cells that contained 522, 1050, and 4999 water molecules as well as one hydroxide ion. The repulsive potential for the oxygen-oxygen pair was improved by iterative Boltzmann inversion, which adjusted the radial distribution function of DFTB-MD simulations to that of the reference density functional theory-MD one. The calculated diffusion coefficients and the Arrhenius diffusion barrier were in good agreement with experimental results. The results of the hydroxide ion coordination number distribution and potential of mean force analyses supported a dynamical hypercoordination diffusion mechanism.

Water-resistant sunscreens for skin protection: an in vivo approach to the two sources of sunscreen failure to maintain UV protection on consumer skin.

The water resistance of sunscreen products has taken more importance for the UV protection of consumers involved in water activities and sports. The present work introduces a new in vivo approach to measure the water resistance of sunscreens on the actual skin of subjects, which can be easily applied to salt, chlorine and tap waters. The stress sources of sunscreen films on skin originate from two phenomena: high surface tension stress as the skin transits through the air/water interface and water diffusion into the film immersed in bulk water. The water resistance of sunscreen products is measured on the forearms of subjects by means of a new layered water bath approach that physically separates both stresses. Tape strips are subsequently taken and analysed for UV-A and UV-B optical densities via (1) imaging for remaining filters and (2) in vitro SPF absorption spectra. Water-resistant sunscreens generally perform well when immersed in bulk water even subjected to agitation, but they show a wide range of performances when considering their behaviour at the air/water interface. The differences are more pronounced in salt water than tap water. The results confirm 2 stress origins in sunscreen exposure to water: interfacial surface tension and bulk water diffusion. Polymers bring improvements to the resistance of sunscreens to bulk water but show wide latitude in performances when subject to the water surface tension stress. Globally, a higher loss of filters is observed in the UV-A than in the UV-B, which is attributed to more UV-A filter loss or degradation and thus resulting in a decreased protection in the UV-A.

Attenuation of diffusive noble-gas transport in laminated sediments of the Stockholm Archipelago

A sediment core has been sampled at a spatial resolution of about two centimeters for noble-gas analysis of the sediment pore water. This high-resolution sampling allowed an excess of dissolved atmospheric gases to be identified in the pore water at a sediment depth of 40 cm. Sedimentological evidence indicates that the observed gas excess is related to a past mass movement that trapped and conserved the gas surplus for more than a century. The measured noble-gas concentrations support the hypothesis that, depending on the sediment texture or particular structures in the sediment, the transport of noble gases in the pore space can be significantly attenuated compared to molecular diffusion in bulk water. The atmospheric noble-gas abundance in the pore water allows the deposition of sediments originally located near the air/water interface to be identified. Although the nature of the physical processes that limit the fluid transport in the pore space could not be fully assessed, our observations indicate that noble-gas concentration profiles can be archived for unexpectedly long times in specific sedimentary sequences. This finding represents a significant step forward in the interpretation of noble-gas concentrations in sediment pore waters in terms of past environmental conditions.

FTIR analysis of a polycarbonate blend after hygrothermal aging

ABSTRACTFourier transform infrared spectroscopy was used to detect changes or degradation in chain structure of PC/ABS specimens after being exposed to three hygrothermal conditions. The two main absorbance peaks of interest are associated with carbonyl and hydroxyl groups due to the oxidation of butadiene in the ABS component. The changes to these groups were evident in earlier work during thermal aging of this blend but were not found in this hygrothermal study. However, the increase in intensity within the hydroxyl region for two of the conditions was attributed to bulk water diffusion in the material. When viewed together with results published earlier by our research group, the changes driven by bulk moisture diffusion are reversible. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41316.

Network analysis of proton transfer in liquid water.

Proton transfer in macromolecular systems is a fascinating yet elusive process. In the last ten years, molecular simulations have shown to be a useful tool to unveil the atomistic mechanism. Notwithstanding, the large number of degrees of freedom involved make the accurate description of the process very hard even for the case of proton diffusion in bulk water. Here, multi-state empirical valence bond molecular dynamics simulations in conjunction with complex network analysis are applied to study proton transfer in liquid water. Making use of a transition network formalism, this approach takes into account the time evolution of several coordinates simultaneously. Our results provide evidence for a strong dependence of proton transfer on the length of the hydrogen bond solvating the Zundel complex, with proton transfer enhancement as shorter bonds are formed at the acceptor site. We identify six major states (nodes) on the network leading from the "special pair" to a more symmetric Zundel complex required for transferring the proton. Moreover, the second solvation shell specifically rearranges to promote the transfer, reiterating the idea that solvation beyond the first shell of the Zundel complex plays a crucial role in the process.

A Reactive Molecular Dynamics Algorithm for Proton Transport in Aqueous Systems

We present a model that incorporates the structural diffusion of a proton into a classical molecular dynamics simulation using a reactive molecular dynamics (RMD) algorithm. The transition state for proton transfer obtained from ab initio calculations is mapped onto a set of geometric and energetic triggers to describe the structural diffusion of the proton in the simulation. Numerical values of these triggers are parametrized to satisfy the experimental values of rate constant and activation energy in order to capture the molecular and macroscopic features of structural diffusion. The algorithm partitions the structural diffusion of a proton into three steps: (i) satisfaction of the triggers, (ii) instantaneous reaction, and (iii) local equilibration. The final step ensures that the ending point of the reaction provides the correct structure and heat of reaction. Hence, the reactivity is incorporated by the algorithm rather than through the development of a reactive potential. We have applied this scheme to study proton transport in bulk water and solutions of HCl. Total charge diffusion along with the structural and vehicular decomposition is studied as a function of temperature (280−320 K). The two components are found to be uncorrelated and the structural diffusion contributes 60−70% of the total charge diffusion in bulk water. The method is applied to HCl solutions (0.22−0.83 M) to study the effect of concentration on proton transport. The reduction in the total diffusivity of the charge with an increase in concentration is due to the reduction in structural diffusion.

Proton transport in water confined in carbon nanotubes: a reactive molecular dynamics study

The effects on the structural and transport properties of a proton in water confined in carbon nanotubes of radii ranging from 5.42 to 10.85 Å were studied by employing a recently devised reactive molecular dynamics (RMD) scheme. The formation of distinct layers was observed in the computed radial density profile of water. Affinity of hydronium ions towards the tube–water interface and its preferential orientation with the oxygen atom protruding towards the wall was observed. The axial water diffusivity was observed to decrease with increasing confinement of water. Analysis of the axial charge diffusivity and its two components (structural and vehicular) was also performed. Confinement was found to have a more significant effect on structural diffusion than on vehicular diffusion. The axial vehicular component of the charge diffusivity in the nanotube of radius 10.85 Å was found to be equal to the value computed in bulk water while structural component was 12% of the value observed in bulk water, which resulted in a total charge diffusivity of 42% of the diffusion in bulk water. The confined geometry affects the system energetically and perturbs the solvation structure around the proton from that found in bulk water. The RMD algorithm, which defines the occurrence of a proton transfer reaction based on the satisfaction of a set of triggers, identified the energetic factor to be greatly responsible for the decreased structural diffusion of a proton.

Diffusion of Na and Cs in montmorillonite

AbstractThe state and dynamics of water and cations in pure and mixed Na-Cs-montmorillonite as a function of the interlayer water content were investigated in the present study, using Monte Carlo and classical, molecular-dynamics methods. While highly idealized, the simulations showed that the swelling behavior of hetero-ionic Na-Cs-montmorillonite is comparable to the swelling of a homo-ionic Na- or Cs-montmorillonite. The mixed Na-Cs-montmorillonite is characterized by intermediate interlayer distances compared to homo-ionic Na- and Cs-montmorillonites. Dry, hetero-ionic Na-Cs-montmorillonite is characterized by a symmetric sheet configuration, as is homo-ionic Cs-montmorillonite.We found that at low degrees of hydration the absolute diffusion coefficient of Cs+ is less than for Na+, whereas at greater hydration states the diffusion coefficient of Cs+ is greaterthan for Na+. An analysis of the relative diffusion coefficients (the ratio between the diffusion coefficient of an ion in the interlayer and its diffusion coefficient in bulk water) revealed that water and Na+ are always less retarded than Cs+. With large interlayer water contents, tetralayer or more, Na+ ions preferentially form outer-sphere complexes. The mobility perpendicular to the clay surface is limited and the diffusion is equivalent to two-dimensional diffusion in bulk water. In contrast, Cs+ ions preferentially form ‘inner-sphere complexes’ at all hydration states and their two-dimensional diffusion coefficient is less than in bulk water.The question remains unanswered as to why experimentally derived relative diffusion coefficients of Cs+ in the interlayer of clays are about 20 times less than those we obtained by classical molecular dynamics studies.

Temperature dependence of protein-hydration hydrodynamics by molecular dynamics simulations

The dynamics of water molecules near the protein surface are different from those of bulk water and influence the structure and dynamics of the protein itself. To elucidate the temperature dependence hydration dynamics of water molecules, we present results from the molecular dynamic simulation of the water molecules surrounding two proteins (Carboxypeptidase inhibitor and Ovomucoid) at seven different temperatures ( T = 273 to 303 K, in increments of 5 K). Translational diffusion coefficients of the surface water and bulk water molecules were estimated from 2 ns molecular dynamics simulation trajectories. Temperature dependence of the estimated bulk water diffusion closely reflects the experimental values, while hydration water diffusion is retarded significantly due to the protein. Protein surface induced scaling of translational dynamics of the hydration waters is uniform over the temperature range studied, suggesting the importance protein–water interactions.

Ocular transport model for ophthalmic delivery of timolol through p-HEMA contact lenses

Approximately 90% of all ophthalmic drug formulations are now applied as eye drops. While eye drops are convenient and well accepted by patients, approximately 95% of the drug contained in the drops is lost due to absorption through the conjunctiva or through tear drainage. Ophthalmic drug delivery via contact lenses should be more effective than drops because it increases the residence time of the drug in the eye, thus leading to a larger fractional intake of the drug through the cornea. While a number of in vivo and some in vitro experiments have been conducted to design and test ophthalmic drug delivery through contact lenses, little quantitative data exists for bioavailability, i.e., the fractional corneal uptake of the drug. In this paper we combine in vitro experiments with modeling to investigate the delivery of timolol, a drug commonly used to treat glaucoma, to the eyes. The in vitro experiments were conducted to create a transport model for releasing the drug from p-HEMA contact lenses. The transport model includes drug adsorption on the polymer and drug diffusion in bulk water. Experiments were conducted at three different cross-linker levels, and the transport parameters were determined for each case. The transport model was then incorporated into a model for the release of the drug from the contact lens into the pre- and post-contact lens tear films and the subsequent corneal uptake. Results show that at least 20% of the timolol entrapped in the lens will enter the cornea, which is much larger than the fractional uptake for drug delivery through drops.

Ab Initio Molecular Dynamics Simulation of the Structure and Proton Transport Dynamics of Methanol−Water Solutions

Ab initio molecular dynamics simulations are employed to study the structural and proton transport properties of methanol-water mixtures. Structural characteristics analyzed at two different methanol mole fractions (X(M) = 0.25 and X(M) = 0.5) reveal enhanced structuring of water as the methanol mole fraction increases in agreement with recent neutron diffraction experiments. The simulations reveal the existence of separate hydrogen-bonded water and methanol networks, also in agreement with the neutron diffraction data. The addition of a single proton to the X(M) = 0.5 mixture leads to an anomalous structural or Grotthuss-type diffusion mechanism of the charge defect in which water-to-water, methanol-to-water, and water-to-methanol proton transfer reactions play the dominant role with methanol-to-methanol transfers being much less significant. Unlike in bulk water, where coordination number fluctuations drive the proton transport process, suppression of the coordination number of waters in the first solvation shell of the defect diminish the importance of coordination number fluctuations as a driving force in the structural diffusion process. The charge defect is found to reside preferentially at the interface between water and methanol networks. The length of the ab initio molecular dynamics run (approximately 120 ps), allowed the diffusion constant of the charge defect to be computed, yielding a value of D = 4.2 x 10(-5) cm2/s when deuterium masses are assigned to all protons in the system. The relation of this value to excess proton diffusion in bulk water is discussed. Finally, a kinetic theory is introduced to identify the relevant time scales in the proton transfer/transport process.