Polarity-dependence of the nonlinear dielectric response in interfacial water.

Molecular dynamics simulations are used to study the nonlinear dielectric responses of a confined aqueous film in a planar nanopore under perpendicular electric fields at varied voltages between confining graphene sheets. Dielectric saturation reminiscent of the bulk phase behavior is prevalent at very strong fields, whereas we observe a nonmonotonic permittivity dependence on the electric field at intermediate strengths where field-alignment and spontaneous polarization of interfacial water are of comparable magnitude. The coupling between the two effects results in distinct dielectric responses at opposite confinement walls. The normal component of both the differential dielectric constant and dielectric difference constant tensors averaged over the region closer to the wall under an incoming electric field (field pointing from the liquid to the solid phase) initially increases with the strength of the imposed field. The differential permittivity peaks at a field strength previously shown to offset the surface-induced orientation bias of hydration molecules at this wall. Further strengthening of the field results in a conventional saturation behavior. At the opposite wall (subject to outgoing field) and in the central region of the water slab, the nonlinear dielectric response resembles bulklike saturation. The conditions at the permittivity extremum coincide with the window of accelerated reorientation rates of interfacial water molecules under an incoming field we uncovered in earlier molecular dynamics analyses.

Correction: Reversible electrowetting transitions on superhydrophobic surfaces.

Correction for 'Reversible electrowetting transitions on superhydrophobic surfaces' by D. Vanzo et al., Phys. Chem. Chem. Phys., 2021, 23, 27005-27013, DOI:10.1039/D1CP04220C.

Reversible electrowetting transitions on superhydrophobic surfaces.

An electric field applied across the interface has been shown to enable transitions from the Cassie to the Wenzel state on superhydrophobic surfaces with miniature corrugations. Molecular dynamics (MD) simulations manifest the possibility of reversible cycling between the two states when narrow surface wells support spontaneous expulsion of water in the absence of the field. With approximately 1 nm sized wells between the surface asperities, the response times to changes in the electric field are of O(0.1) ns, allowing up to GHz frequency of the cycle. Because of the orientation preferences of interfacial water in contact with the solid, the phenomenon depends on the polarity of the field normal to the interface. The threshold field strength for the Cassie-to-Wenzel transition is significantly lower for the field pointing from the aqueous phase to the surface; however, once in the Wenzel state, the opposite field direction secures tighter filling of the wells. Considerable hysteresis revealed by the delayed water retraction at decreasing field strength indicates the presence of moderate kinetic barriers to expulsion. Known to scale approximately with the square of the length scale of the corrugations, these barriers preclude the use of increased corrugation sizes while the reduction of the well diameter necessitates stronger electric fields. Field-controlled Cassie-to-Wenzel transitions are therefore optimized by using superhydrophobic surfaces with nanosized corrugations. Abrupt changes indicate a high degree of cooperativity reflecting the correlations between the wetting states of interconnected wells on the textured surface.

Molecular polarizability in open ensemble simulations of aqueous nanoconfinements under electric field.

Molecular polarization at aqueous interfaces involves fast degrees of freedom that are often averaged-out in atomistic-modeling approaches. The resulting effective interactions depend on a specific environment, making explicit account of molecular polarizability particularly important in solutions with pronounced anisotropic perturbations, including solid/liquid interfaces and external fields. Our work concerns polarizability effects in nanoscale confinements under electric field, open to an unperturbed bulk environment. We model aqueous molecules and ions in hydrophobic pores using the Gaussian-charge-on-spring BK3-AH representation. This involves nontrivial methodology developments in expanded ensemble Monte Carlo simulations for open systems with long-ranged multibody interactions and necessitates further improvements for efficient modeling of polarizable ions. Structural differences between fixed-charge and polarizable models were captured in molecular dynamics simulations for a set of closed systems. Our open ensemble results with the BK3 model in neat-aqueous systems capture the ∼10% reduction of molecular dipoles within the surface layer near the hydrophobic pore walls in analogy to reported quantum mechanical calculations at water/vapor interfaces. The polarizability affects the interfacial dielectric behavior and weakens the electric-field dependence of water absorption at pragmatically relevant porosities. We observe moderate changes in thermodynamic properties and atom and charged-site spatial distributions; the Gaussian distribution of mobile charges on water and ions in the polarizable model shifts the density amplitudes and blurs the charge-layering effects associated with increased ion absorption. The use of polarizable force field indicates an enhanced response of interfacial ion distributions to applied electric field, a feature potentially important for in silico modeling of electric double layer capacitors.

Electrokinetic flow of an aqueous electrolyte in amorphous silica nanotubes.

We study the pressure-driven flow of aqueous NaCl in amorphous silica nanotubes using nonequilibrium molecular dynamics simulations featuring both polarizable and non-polarizable molecular models. Different pressures, electrolyte concentrations and pore sizes are examined. Our results indicate a flow that deviates considerably from the predictions of Poiseuille fluid mechanics. Due to preferential adsorption of the different ionic species by surface SiO- or SiOH groups, we find that a significant electric current is generated, but with opposite polarities using polarizable vs. fixed charge models for water and ions, emphasizing the need for careful parameterization in such complex systems. We also examine the influence of partial deprotonation of the silica surface, and we find that much more current is generated in a dehydrogenated nanopore, even though the overall efficiency remains low. These findings indicate that different methods of nanopore preparation, which can produce a range of surface properties, should be examined more closely in the related experimental methods to generate electrokinetic current.

Nanoconfined water under electric field at constant chemical potential undergoes electrostriction.

Electric control of nanopore permeation by water and solutions enables gating in membrane ion channels and can be exploited for transient surface tuning of rugged substrates, to regulate capillary permeability in nanofluidics, and to facilitate energy absorption in porous hydrophobic media. Studies of capillary effects, enhanced by miniaturization, present experimental challenges in the nanoscale regime thus making molecular simulations an important complement to direct measurement. In a molecular dynamics (MD) simulation, exchange of water between the pores and environment requires modeling of coexisting confined and bulk phases, with confined water under the field maintaining equilibrium with the unperturbed environment. In the present article, we discuss viable methodologies for MD sampling in the above class of systems, subject to size-constraints and uncertainties of the barostat function under confinement and nonuniform-field effects. Smooth electric field variation is shown to avoid the inconsistencies of MD integration under abruptly varied field and related ambiguities of conventional barostatting in a strongly nonuniform interfacial system. When using a proper representation of the field at the border region of the confined water, we demonstrate a consistent increase in electrostriction as a function of the field strength inside the pore open to a field-free aqueous environment.

Specific ion effects in solutions of globular proteins: comparison between analytical models and simulation.

Monte Carlo simulations have been performed for ion distributions outside a single globular macroion and for a pair of macroions, in different salt solutions. The model that we use includes both electrostatic and van der Waals interactions between ions and between ions and macroions. Simulation results are compared with the predictions of the Ornstein-Zernike equation with the hypernetted chain closure approximation and the nonlinear Poisson-Boltzmann equation, both augmented by pertinent van der Waals terms. Ion distributions from analytical approximations are generally very close to the simulation results. This demonstrates that properties that are related to ion distributions in the double layer outside a single interface can to a good approximation be obtained from the Poisson-Boltzmann equation. We also present simulation and integral equation results for the mean force between two globular macroions (with properties corresponding to those of hen-egg-white lysozyme protein at pH 4.3) in different salt solutions. The mean force and potential of mean force between the macroions become more attractive upon increasing the polarizability of the counterions (anions), in qualitative agreement with experiments. We finally show that the deduced second virial coefficients agree quite well with experimental results.

National character does not reflect mean personality trait levels in 49 cultures.

Most people hold beliefs about personality characteristics typical of members of their own and others' cultures. These perceptions of national character may be generalizations from personal experience, stereotypes with a "kernel of truth," or inaccurate stereotypes. We obtained national character ratings of 3989 people from 49 cultures and compared them with the average personality scores of culture members assessed by observer ratings and self-reports. National character ratings were reliable but did not converge with assessed traits. Perceptions of national character thus appear to be unfounded stereotypes that may serve the function of maintaining a national identity.

Phase behavior of aqueous solutions containing dipolar proteins from second-order perturbation theory.

Due to the interplay of Coulombic repulsion and attractive dipolar and van der Waals interactions, solutions of globular proteins display a rich variety of phase behavior featuring fluid-fluid and fluid-solid transitions that strongly depend on solution pH and salt concentration. Using a simple model for charge, dispersion and dipole-related contributions to the interprotein potential, we calculate phase diagrams for protein solutions within the framework of second-order perturbation theory. For each phase, we determine the Helmholtz energy as the sum of a hard-sphere reference term and a perturbation term that reflects both the electrostatic and dispersion interactions. Dipolar effects can induce fluid-fluid phase separation or crystallization even in the absence of any significant dispersion attraction. Because dissolved electrolytes screen the charge-charge repulsion more strongly than the dipolar attraction, the ionic strength dependence of the potential of mean force can feature a minimum at intermediate ionic strengths offering an explanation for the observed nonmonotonic dependence of the phase behavior on salt concentration. Inclusion of correlations between charge-dipole and dipole-dipole interactions is essential for a reliable calculation of phase diagrams for systems containing charged dipolar proteins and colloids.

Electrostatic interactions of charged dipolar proteins in reverse micelles.

The electrostatic interactions in a reverse micelle containing a small-ionized protein are studied by Monte Carlo simulation. The electrostatic contribution to the potential of mean force of the protein in the reverse micelle is determined for a neutral protein, a uniformly charged protein, and a uniformly charged protein with a dipole moment. The effect of addition of a simple electrolyte is studied. While symmetrically distributed micellar charge exerts no force on enclosed ionic species, the protein is driven to the micellar wall due to interactions with simple ions. Protein binding to the inner wall of the micelle can be regulated by added salt. The presence of a dipole drives the protein further to the wall. These effects are studied for several proteins characterized by different charges and dipole moments. For a weakly charged protein with a strong dipole moment the contribution of dipolar interaction to the free energy can represent a major driving force for protein solubilization in the microemulsion.

Interaction between oppositely charged micelles or globular proteins.

Monte Carlo simulations and the hypernetted chain theory are used to study the interaction between spherical macroions of opposite charge immersed in a solution of monovalent or divalent simple electrolyte. These calculations represent the first step toward studying phase behavior and precipitation kinetics in solutions containing a mixture of macroions with positive and negative net charges. The potential of mean force between colloidal particles is determined as a function of colloid-colloid separation. In addition to having an opposite sign, the calculated potential of mean force is found to be stronger and longer-ranged than observed in the case of equally charged macroparticles. The difference is more pronounced in the presence of divalent counterions and is especially noticeable when we compare distinct Coulombic and hard-core collision contributions to the interaction between equally and oppositely charged colloids. The present observations suggest the dominance of attractive forces between globally neutral but electrostatically heterogeneous macroparticles. While our numerical results cannot be successfully analyzed by existing theories, they provide useful guidance and benchmark data for the development of advanced analytic descriptions.

Age differences in personality across the adult life span: parallels in five cultures.

Both cross-sectional and longitudinal studies in the United States have shown consistent changes between college age and middle adulthood. There appear to be declines in 3 of the 5 major factors of personality--Neuroticism, Extraversion, and Openness--and increases in Agreeableness and Conscientiousness. To examine cross-cultural generalizability of these findings, translations of the Revised NEO Personality Inventory were administered to samples in Germany, Italy, Portugal, Croatia, and South Korea (N = 7,363). Similar patterns of age differences were seen in each country, for both men and women. Common trends were also seen for the more specific traits that define the major factors. Because these nations differ substantially in culture and recent history, results suggest the hypothesis that these are universal maturational changes in adult personality.

Interaction between like-charged colloidal spheres in electrolyte solutions.

How colloidal particles interact with each other is one of the key issues that determines our ability to interpret experimental results for phase transitions in colloidal dispersions and our ability to apply colloid science to various industrial processes. The long-accepted theories for answering this question have been challenged by results from recent experiments. Herein we show from Monte-Carlo simulations that there is a short-range attractive force between identical macroions in electrolyte solutions containing divalent counterions. Complementing some recent and related results by others, we present strong evidence of attraction between a pair of spherical macroions in the presence of added salt ions for the conditions where the interacting macroion pair is not affected by any other macroions that may be in the solution. This attractive force follows from the internal-energy contribution of counterion mediation. Contrary to conventional expectations, for charged macroions in an electrolyte solution, the entropic force is repulsive at most solution conditions because of localization of small ions in the vicinity of macroions. Both Derjaguin-Landau-Verwey-Overbeek theory and Sogami-Ise theory fail to describe the attractive interactions found in our simulations; the former predicts only repulsive interaction and the latter predicts a long-range attraction that is too weak and occurs at macroion separations that are too large. Our simulations provide fundamental "data" toward an improved theory for the potential of mean force as required for optimum design of new materials including those containing nanoparticles.