Controllable transport of water through nanochannel by rachet-like mechanism

By using molecular dynamics simulation, we have investigated systematically the feasibility of continuous unidirectional water flux across a deformed single-walled carbon nanotube (SWNT) driven by an oscillating charge outside without osmotic pressure or hydrostatic drop. Simulation results indicate that the flux is dependent sensitively on the oscillating frequency of the charge, the distance of the charge from the SWNT, and the asymmetry of the water-SWNT system. A resonance-like phenomenon is found that the water flux is enhanced significantly when the period of the oscillation is close to twice the average hopping time of water molecules inside the SWNT. These findings are helpful in developing a novel design of efficient functional nanofluidic devices.     

Chemistry in nanochannel confinement

This review addresses the questions of whether it makes sense to use lithographically defined nanochannels for chemistry in liquids, and what it is possible to learn from experiments on that topic. The behavior of liquids in different classes of pores (categorized according to their size) is reviewed, with a focus on chemical reactions and protein dynamics. A number of interesting phenomena are discussed for nanochannels with feature sizes that are manufacturable with modern photolithography-based fabrication technology. The use of spectroscopic methods to investigate chemistry in nanochannels, where both spectroscopic method and nanochannels are integrated into a single device, will be evaluated.     

Effects of water nanochannel diameter on proton transport in proton‐exchange membranes

The effects of water nanochannel diameter on proton transport pathways and properties have been studied using reactive molecular dynamics simulations. The proton distributions and diffusivities have been evaluated using the cylinder model of water domains at various diameters that is the most typical proposed morphological model in proton‐exchange membranes. The proton distributions are analyzed to clarify proton pathways by classifying the water channel into two regions in parallel: an inner channel (free water) and an outer channel (bound water). For all the water contents, the nonmonotonic trends that show a peak at a certain diameter are found to be observed in the proton diffusivity, which is dominated by the proton diffusivity in the free water region and has a strong correlation with the proton distribution that is controlled by the balance between the volume fraction of free water and the surface density of sulfonate groups. The electroosmotic drag coefficients are found to increase monotonically with increasing channel diameter as a result of the increase in the volume fraction of free water. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 867–878     

Entrapment of organic solutes by the water cage in the nanochannel of MCM-41

The effect of MCM-41 on the ESR spectrum of an aqueous spin probe solution was observed. The sharp ESR spectrum turns into a rather broad characteristic one leaving a sharper signal as the minor component, immediately after the addition of MCM-41 powder to the system. This observation indicates that MCM-41 traps the solute molecule into the nanochannel by letting the solvent water form a rather stable molecular cage, since the ESR line shape indicates that the nitroxide radical undergoes anisotropic rotation without being adsorbed on the wall. Thermodynamic parameters for this process are estimated from the temperature dependencies of the trapping efficiency. This process is explained in terms of the surface enthalpy of the liquid specifically intensified in the nanospace.     

Speciation of silica in high-purity water

A 1-l water sample was concentrated to 20ml by freezing and analyzed for soluble, colloidal and insoluble silica by the spectrophotometric heteropoly blue method and by inductively coupled plasma/atomic emission spectrometry. High-purity water obtained from a vitreous-silica sub-boiling distillation still contained a few micrograms of insoluble silica per liter.     

Solute transport and separation in nanochannel chromatography

An analytical model is developed to study the solute transport and separation in pressure-driven liquid flow through cylindrical nanochannels. The flow-induced streaming potential is found to significantly affect the solute speed, retention and dispersion in nanochannel chromatography. These effects are sensitive to the solute charge, and found to be mainly dependent on an electrokinetic "figure of merit".     

Structural analysis of water adsorbed in silica gel

The melting point, T _f of water in a pore decreases as the surface area to pore volume ratio of the pore decreases. Analysis of water absorbed in the pores of silica gels using differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS) shows that the thickness of the bound, non-freezing water layer adjacent to the pore surface increases as its temperature increases, but that it is independent of the surface silanol concentration, [Si_sOH]. In contrast, the thickness decreases as the cylindrical pore radius r _H decreases. Thus, the increase in the bound water thickness from 0.45 nm for gels with r _H =1.2 nm to 1.2 nm for gels with r _H =7.5 nm is due to the increase from –53°C to –7°C of the temperature (e.g., the melting point T _f ) at which the bound water thickness was measured, and not due to the increase in t _H or the decrease in [Si_sOH]. The T _f of bulk water measured in a DSC was –0.3°C. The boiling point T _v of bulk water measured in a DSC was 81.3°C. T _v increased to 94°C in 7.5 nm pores and to 109°C K in 1.2 nm pores.     

Cleavage and recovery of molecular water in silica

The network response associated with the incorporation and reactivity of water molecules in bulk phases of amorphous and crystalline silica are investigated using density functional theory. The extent of network relaxation is found to change the relative stabilities of the reactant and product states. A highly reactive site, with a low activation barrier, is associated with a highly strained site in which network relaxation significantly stabilizes the silanol state by effectively annealing the local structure. Diffusion and exchange reaction paths are found to likely be associated with minimum energy paths in which the stability of the product and reactant states are equal. These latter paths are associated with minimal network response, although the ability of the silanol groups to take on several conformations has an overall effect of changing the stability along a given reaction path.     

Influence of viscoelectric effect on diffusioosmotic transport in nanochannel

We have investigated the role of viscoelectric effect on diffusioosmotic flow (DOF) through a nanochannel connected with two reservoirs. The transport equations governing the flow dynamics are solved numerically using the finite element technique. We have extensively analyzed the variation of induced field due to electric double layer (EDL) phenomenon, relative viscosity as modulated by the viscoelectric effect as well as reservoir's concentration difference, and their eventual impact on the underlying flow characteristics. It is revealed that the induced electric field in the EDL enhances fluid viscosity substantially near the charged wall at a higher concentration. We have shown that neglecting viscoelectric effect in the paradigm of diffusioosmotic transport overestimates the net throughput, particularly at a higher concentration difference. Furthermore, we show that pertaining to chemiosmosis dominated regime, the average flow velocity modifies with the increase in concentration difference up to a critical value. In comparison, the rise in the strength of resistive electroosmotic actuation by the accumulation of anions in the upstream reservoir reduces the average flow velocity at a higher concentration difference. We have reported a reduction in critical concentration with the increase in viscoelectric effect. The inferences of this analysis are deemed pertinent to reveal the bearing of viscoelectric effect as a flow control mechanism pertaining to DOF at nanoscale.     

Melting and freezing of water in cylindrical silica nanopores

Freezing and melting of H(2)O and D(2)O in the cylindrical pores of well-characterized MCM-41 silica materials (pore diameters from 2.5 to 4.4 nm) was studied by differential scanning calorimetry (DSC) and (1)H NMR cryoporometry. Well-resolved DSC melting and freezing peaks were obtained for pore diameters down to 3.0 nm, but not in 2.5 nm pores. The pore size dependence of the melting point depression DeltaT(m) can be represented by the Gibbs-Thomson equation when the existence of a layer of nonfreezing water at the pore walls is taken into account. The DSC measurements also show that the hysteresis connected with the phase transition, and the melting enthalpy of water in the pores, both vanish near a pore diameter D* approximately equal to 2.8 nm. It is concluded that D* represents a lower limit for first-order melting/freezing in the pores. The NMR spin echo measurements show that a transition from low to high mobility of water molecules takes place in all MCM-41 materials, including the one with 2.5 nm pores, but the transition revealed by NMR occurs at a higher temperature than indicated by the DSC melting peaks. The disagreement between the NMR and DSC transition temperatures becomes more pronounced as the pore size decreases. This is attributed to the fact that with decreasing pore size an increasing fraction of the water molecules is situated in the first and second molecular layers next to the pore wall, and these molecules have slower dynamics than the molecules in the core of the pore.     

Interaction between water and defective silica surfaces

We use the density functional theory method to study dry (1 × 1) α-quartz (0001) surfaces that have Frenkel-like defects such as oxygen vacancy and oxygen displacement. These defects have distinctively different effects on the water-silica interface depending on whether the adsorbent is a single water molecule, a cluster, or a thin film. The adsorption energies, bonding energies, and charge transfer or redistributions are analyzed, from which we find that the existence of a defect enhances the water molecule and cluster surface interaction by a large amount, but has little or even negative effect on water thin film-silica surface interaction. The origin of the weakening in film-surface systems is the collective hydrogen bonding that compromises the water-surface interaction in the process of optimizing the total energy. For clusters on surfaces, the lowest total energy states lower both the bonding energy and the adsorption energy.     

Structure and dynamics of water confined in silica nanopores

We report the results of molecular simulation of water in silica nanopores at full hydration and room temperature. The model systems are approximately cylindrical pores in amorphous silica, with diameters ranging from 20 to 40 ?. The filled pores are prepared using grand canonical Monte Carlo simulation and molecular dynamics simulation is used to calculate the water structure and dynamics. We found that water forms two distinct molecular layers at the interface and exhibits uniform, but somewhat lower than bulk liquid, density in the core region. The hydrogen bond density profile follows similar trends, with lower than bulk density in the core and enhancements at the interface, due to hydrogen bonds between water and surface non-bridging oxygens and OH groups. Our studies of water dynamics included translational mean squared displacements, orientational time correlations, survival probabilities in interfacial shells, and hydrogen bond population relaxation. We found that the radial-axial anisotropy in translational motion largely follows the predictions of a model of free diffusion in a cylinder. However, both translational and rotational water mobilities are strongly dependent on the proximity to the interface, with pronounced slowdown in layers near the interface. Within these layers, the effects of interface curvature are relatively modest, with only a small increase in mobility in going from the 20 to 40 ? diameter pore. Hydrogen bond population relaxation is nearly bulk-like in the core, but considerably slower in the interfacial region.     

Longitudinal and volume viscosities of fluids confined in nanochannel

Longitudinal and volume viscosities of Lennard-Jones fluid, argon–krypton binary mixture and isotopic fluid mixture confined to nanochannels of different widths are calculated by employing theoretical technique based on Green–Kubo formula. A significant enhancement is observed in longitudinal and volume viscosities when width of the nanochannel is less than 10 nm. Effect of mass ratio of two species on longitudinal and volume viscosities is also studied for equimolar isotopic fluid mixture. It is found that enhancement in viscosity is more for larger mass ratios. It is also noted that enhancement in longitudinal and shear viscosities is more than volume viscosity.     

Electrokinetic ion transport in confined micro‐nanochannel

In this paper, a confined micronanochannel is presented to concentrate ions in a restricted zone. A general model exploiting the Poisson–Nernst–Plank equations coupled with the Navier–Stokes equation is employed to simulate the electrokinetic ion transport. The influences of the micronanochannel dimension and the surface charge density on the potential distribution, the ion concentration, and the fluid flow are investigated. The numerical results show that the potential drop depends mainly on the nanochannel, instead of the confined channel. Both decreasing the width and increasing the length enhance the ion enrichment performance. For a given nanochannel, ultimate value of ion concentration may be determined by the potential at the center point of the nanochannel. The study also shows that the enrichment stability can be improved by increasing the micronanochannel width, decreasing the micronanochannel length and reducing the surface charge density.     

Proton quantum coherence observed in water confined in silica nanopores

Deep inelastic neutron scattering measurements of water confined in nanoporous xerogel powders, with average pore diameters of 24 and 82 A, have been carried out for pore fillings ranging from 76% to nearly full coverage. DINS measurements provide direct information on the momentum distribution n(p) of protons, probing the local structure of the molecular system. The observed scattering is interpreted within the framework of the impulse approximation and the longitudinal momentum distribution determined using a model independent approach. The results show that the proton momentum distribution is highly non-Gaussian. A bimodal distribution appears in the 24 A pore, indicating coherent motion of the proton over distances d of approximately 0.3 A. The proton mean kinetic energy W of the confined water molecule is determined from the second moment of n(p). The W values, higher than in bulk water, are ascribed to changes of the proton dynamics induced by the interaction between interfacial water and the confining surface.     

Electroviscous effect on the streaming current in a pH-regulated nanochannel

Accurate and rapid estimation of the streaming current in nanochannels is crucial for the development of the nanofluidics based power generation apparatus. In this study, an analytical model is developed for the first time to examine the electroviscous effect on the streaming current/conductance in a pH-regulated nanochannel by considering practical effects of multiple ionic species, surface chemistry reactions, and the Stern layer. Predictions from the model are in good agreement with the experimental results of the streaming conductance in silica nanochannels available in the literature. The electroviscous effect could have a significant reduction of ca. 30% in the streaming conductance at medium pH and low salt concentration.     

Nanowells on silica particles in water containing long-distance porphyrin heterodimers

Smooth and nonswelling spherical silica particles with a diameter of 100 nm and an aminopropyl coating are soluble in water at pH 11, coagulate quickly at pH 3, and redissolve at pH 9. Electron microscopy as well as visible spectra of covalently attached porphyrins indicate the aggregation state of the particles. Long-chain alpha,omega-dicarboxylic acids with a terminal oligoethyleneglycol (=OEG)-amide group were attached in a second self-assembly step to the remaining amine groups around the porphyrins. Form-stable 2-nm wells were thus obtained and were characterized by fluorescence quenching experiments using the bottom porphyrin as a target. The one-dimensional diffusion of fitting quencher molecules along the 2-nm pathway took several minutes. Porphyrins with a diameter above 2 nm could not enter the form-stable gaps at all. Added tyrosine stuck irreversibly to the walls of the nanowells and prevented the entrance of quencher molecules, the OEG-headgroups fixated 2,6-diaminoanthraquinone. A ring of methylammonium groups was then fixed at the walls of the wells at a distance of 5 or 10 A with respect to the bottom porphyrin. 2,6-Disulfonatoanthraquinone was attached only loosely to this ring, but the exactly fitting manganese(III) meso-(tetraphenyl-4-sulfonato)porphyrinate (Mn(III) TPPS) was tightly bound. Transient fluorescence experiments showed a fast decay time of 0.2 ns for the bottom porphyrin, when the Mn(III) TPPS was fixated at a distance of 5 A. Two different dyes have thus been immobilized at a defined subnanometer distance in an aqueous medium.     

Interaction of single water molecules with silanols in mesoporous silica

Deep Inelastic Neutron Scattering measurements of water confined in mesoporous silica have been carried out. The experiment has been performed at room temperature on dry and on hydrated samples in order to investigate the interaction between the protons and the silanol groups of the confining surface. With this aim we could control the hydration of the pores in such a way as to adsorb 3.0 water molecules per nm(2), corresponding to a 1 to 1 ratio with the silanol groups of the surface. DINS measurements directly measure the mean kinetic energy and the momentum distribution of the protons. A detailed analysis of the hydrated sample has been performed in order to separate the contributions of the protons in the system, allowing us to determine the arrangement of water molecules on the silanol groups. We find that the hydrogen bond of the water proton with the oxygen of the silanol group is much stronger than the hydrogen bonds of bulk water.