We investigate the solvation of methane and methane decorated with charges in spherically confined water droplets. Free energy profiles for a single methane molecule in droplets, ranging in diameter D, from 1 to 4 nm, show that the droplet surfaces are strongly favorable as compared to the interior. From the temperature dependence of the free energy in D=3 nm, we show that this effect is entropically driven. The potentials of mean force (PMFs) between two methane molecules show that the solvent separated minimum in the bulk is completely absent in confined water, independent of the droplet size since the solute particles are primarily associated with the droplet surface. The tendency of methanes with charges (Mq+ and Mq- with q+ = q- = 0.4e, where e is the electronic charge) to be pinned at the surface depends dramatically on the size of the water droplet. When D=4 nm, the ions prefer the interior whereas for D<4 nm the ions are localized at the surface, but with much less tendency than for methanes. Increasing the ion charge to e makes the surface strongly unfavorable. Reflecting the charge asymmetry of the water molecule, negative ions have a stronger preference for the surface compared to positive ions of the same charge magnitude. With increasing droplet size, the PMFs between Mq+ and Mq- show decreasing influence of the boundary due to the reduced tendency for surface solvation. We also show that as the solute charge density decreases the surface becomes less unfavorable. The implications of our results for the folding of proteins in confined spaces are outlined.
Water and water-mediated interactions determine thermodynamic and kinetics of protein folding, protein aggregation and self-assembly in confined spaces. To obtain insights into the role of water in the context of folding problems, we describe computer simulations of a few related model systems. The dynamics of collapse of eicosane shows that upon expulsion of water the linear hydrocarbon chain adopts an ordered helical hairpin structure with 1.5 turns. The structure of dimer of eicosane molecules has two well ordered helical hairpins that are stacked perpendicular to each other. As a prelude t…
Room temperature ionic liquids show potential as an alternative to conventional organic membrane solvents mainly due to their properties of low vapor pressure, low volatility and they are often stable. In the present work, the technical feasibilities of room temperature ionic liquids as bulk liquid membranes for phenol removal were investigated experimentally. Three ionic liquids with high hydrophobicity were used and their phenol removal efficiency, membrane stability and membrane loss were studied. Besides that, the effects of several parameters, namely feed phase pH, feed concentration, NaO…
Fundamental understanding of ionic transport at the nanoscale is essential for developing biosensors based on nanopore technology and new generation high-performance nanofiltration membranes for separation and purification applications. We study here ionic transport through single putatively neutral hydrophobic nanopores with high aspect ratio (of length L=6 μm with diameters ranging from 1 to 10 nm) and with a well controlled cylindrical geometry. We develop a detailed hybrid mesoscopic theoretical approach for the electrolyte conductivity inside nanopores, which considers explicitly ion adve…
Fundamental studies of the effect of specific ions on hydrophobic interactions are driven by the need to understand phenomena such as hydrophobically driven self-assembly or protein folding. Using beta-peptide-inspired nano-rods, we investigate the effects of both free ions (dissolved salts) and proximally immobilized ions on hydrophobic interactions. We find that the free ion effect is correlated with the water density fluctuation near a non-polar molecular surface, showing that such fluctuation can be an indicator of hydrophobic interactions in the case of solution additives. In the case of …
While individual water molecules adsorb strongly on a talc surface (hydrophilic behavior), a droplet of water beads up on the same surface (hydrophobic behavior). To rationalize this dichotomy, we investigate the influence of the microscopic structure of the surface and the strength of adhesive (surface-water) interactions on surface hydrophobicity. We show that at low relative humidity, the competition between adhesion and the favorable entropy of being in the vapor phase determines the surface coverage. However, at saturation, it is the competition between adhesion and cohesion (water-water …
Humid hydrophobic ionic liquids, widely used as electrolytes, have narrowed electrochemical windows, because their water, absorbed on the electrode surface, gets involved in electrolysis. In this work, we performed molecular dynamics simulations to explore effects of adding Li-salt in humid ionic liquids on the water adsorbed on the electrode surface. Results reveal that most of water molecules are pushed away from both cathode and anode, by adding salt. The water remained on the electrode is almost bound with Li+, which has significantly lowered activity. The Li+-bonding and re-arrangement of…
Graphene-based electric power generation that converts mechanical energy of flow of ionic droplets over the device surface into electricity has emerged as promising candidate for a blue-energy network. Yet the lack of a microscopic understanding of the underlying mechanism has prevented ability to optimize and control the performance of such devices. This requires information on interfacial structure and charging behavior at the molecular level. Here, we use sum-frequency vibrational spectroscopy (SFVS) to probe the interfaces of devices composed of aqueous solution, graphene and supporting po…
The heterogeneous oxidation reaction of single aqueous ascorbic acid (AH$_2$) aerosol particles with gas-phase ozone was investigated in this study utilizing aerosol optical tweezers with Raman spectroscopy. The measured liquid-phase bimolecular rate coefficients of the AH$_2$ + O$_3$ reaction exhibit a significant pH dependence, and the corresponding values at ionic strength 0.2 M are $(3.1 \pm 2.0) \times 10^5$ M$^{-1}$s$^{-1}$ and $(1.2 \pm 0.6) \times 10^7$ M$^{-1}$s$^{-1}$ for pH $\approx$ 2 and 6, respectively. These results measured in micron-sized droplets agree with those from previou…
Earlier works found out spontaneous directional motion of liquid droplets on hydrophilic conical surfaces, however, not hydrophobic case. Here we show that droplets on any surface may take place spontaneous directional motion without considering contact angle property. The driving force is found to be proportional to the curvature gradient of the surface. Fast motion can be lead at surfaces with small curvature radii. The above discovery can help to create more effective transportation technology of droplets, and better understand some observed natural phenomena.
We have used molecular dynamics simulations to study the effect of water on the wetting behavior and the interfacial structure of ionic liquid (IL) 1-ethyl-3-methylimidazolium boron tetrafluoride[EMIM][BF4] droplets on graphite surfaces which, is a prerequisite for the new IL-based applications in the field of chemical engineering. A slight decrement in the value of the contact angle has been found while adding water up to 20wt%; afterward, the contact angle starts to increase. The non-monotonic behavior of contact angle of IL droplet with the addition of water molecules was examined through s…
The structure and nature of water confined between hydrophobic molybdenum disulfide (MoS2) and graphene (Gr) are investigated at room temperature by means of atomic force microscopy. We find the formation of two-dimensional (2D) crystalline ice layers. In contrast to the hexagonal ice 'bilayers' of bulk ice, these 2D crystalline ice phases consist of two planar hexagonal layers. Additional water condensation leads to either lateral expansion of the ice layers or to the formation of three-dimensional water droplets on top or at the edges of the two-layer ice, indicating that water does not wet …
Making liquid droplets move spontaneously on solid surfaces is a key challenge in lab-on-chip and heat exchanger technologies. The best-known mechanism, a wettability gradient, does not generally move droplets rapidly enough and cannot drive droplets smaller than a critical size. Here we report how a curvature gradient is particularly effective at accelerating small droplets, and works for both hydrophilic and hydrophobic surfaces. Experiments for water droplets on tapered surfaces with curvature radii in the sub-millimeter range show a maximum speed of 0.28 m/s, two orders of magnitude higher…
We directly observed molecular-thick aqueous salt-solution pancakes on a hydrophobic graphite surface under ambient conditions employing atomic force microscopy. This observation indicates the unexpected molecular-scale hydrophilicity of the salt solution on graphite surfaces, which is different from the macroscopic wetting property of a droplet standing on the graphite surface. Interestingly, the pancakes spontaneously displayed strong positively charged behavior. Theoretical studies showed that the formation of such positively charged pancakes is attributed to cation-π interactions between N…
The number of precise conductance measurements in nanopores is quickly growing. In order to clarify the dominant mechanisms at play and facilitate the characterization of such systems for which there is still no clear consensus, we propose an analytical approach to the ionic conductance in nanopores that takes into account (i) electro-osmotic effects, (ii) flow slip at the pore surface for hydrophobic nanopores, (iii) a component of the surface charge density that is modulated by the reservoir $p$H and salt concentration $c_s$ using a simple charge regulation model, and (iv) a fixed surface ch…
Polyelectrolyte multilayers (PEM) in combination with good electrolyte solvents, e.g., ionic liquids (ILs) are potential candidates for the new generation of electrochemical separators. Swelling PEM with aqueous IL solutions is one way to incorporate IL in PEM. In addition to quantifying the IL uptake in PEM, physical characterization of the swollen PEM is essential for their potential applications and to uncover the underlying molecular process of the swelling. In this article, thickness and viscoelasticity of PEI(PSS/PADMAC)4PSS and PEI(PSS/PAH)4PSS multilayers were determined upon uptake of…
Rough or textured hydrophobic surfaces are dubbed superhydrophobic due to their numerous desirable properties, such as water repellency and interfacial slip. Superhydrophobicity stems from an aversion for water to wet the surface texture, so that a water droplet in the superhydrophobic "Cassie state", contacts only the tips of the rough hydrophobic surface. However, superhydrophobicity is remarkably fragile, and can break down due to the wetting of the surface texture to yield the "Wenzel state" under various conditions, such as elevated pressures or droplet impact. Moreover, due to large ener…
