Multiscale Modeling of Aqueous Electric Double Layers.

From the stability of colloidal suspensions to the charging of electrodes, electric double layers play a pivotal role in aqueous systems. The interactions between interfaces, water molecules, ions and other solutes making up the electrical double layer span length scales from Ångströms to micrometers and are notoriously complex. Therefore, explaining experimental observations in terms of the double layer's molecular structure has been a long-standing challenge in physical chemistry, yet recent advances in simulations techniques and computational power have led to tremendous progress. In particular, the past decades have seen the development of a multiscale theoretical framework based on the combination of quantum density functional theory, force-field based simulations and continuum theory. In this Review, we discuss these theoretical developments and make quantitative comparisons to experimental results from, among other techniques, sum-frequency generation, atomic-force microscopy, and electrokinetics. Starting from the vapor/water interface, we treat a range of qualitatively different types of surfaces, varying from soft to solid, from hydrophilic to hydrophobic, and from charged to uncharged.

Ostwald ripening of aqueous microbubble solutions.

Bubble solutions are of growing interest because of their various technological applications in surface cleaning, water treatment, and agriculture. However, their physicochemical properties, such as the stability and interfacial charge of bubbles, are not fully understood yet. In this study, the kinetics of radii in aqueous microbubble solutions are experimentally investigated, and the results are discussed in the context of Ostwald ripening. The obtained distributions of bubble radii scaled by mean radius and total number were found to be time-independent during the observation period. Image analysis of radii kinetics revealed that the average growth and shrinkage speed of each bubble is governed by diffusion-limited Ostwald ripening, and the kinetic coefficient calculated using the available physicochemical constants in the literature quantitatively agrees with the experimental data. Furthermore, the cube of mean radius and mean volume exhibit a linear time evolution in agreement with the Lifshitz-Slezov-Wagner (LSW) theory. The coefficients are slightly larger than those predicted using the LSW theory, which can be qualitatively explained by the effect of finite volume fraction. Finally, the slowdown and pinning of radius in the shrinkage dynamics of small microbubbles are discussed in detail.

Electrophoretic Mobility of a Water-in-Oil Droplet Separately Affected by the Net Charge and Surface Charge Density.

Water-in-oil emulsions and droplets exhibit physicochemical properties completely different from those of oil-in-water emulsions and droplets. Thus, directly applying a standard theoretical model to water-in-oil systems cannot describe these anomalous properties. Here, the electrophoretic mobility of a water-in-oil droplet is analytically investigated using Debye-Hückel linearization and neglecting the Marangoni effect. The resulting electrophoretic mobility is shown to be separately dependent on the net charge of the droplet and the surface charge density at the droplet interface. Furthermore, when the net charge is negligible, the electrophoretic mobility is proportional to the surface charge density with a negative coefficient. This indicates that the internal electric double layer inversely contributes to the electrophoresis. This theory is applied to experimental data of water-in-oil emulsions and droplets in the literature, and qualitative and quantitative verification of the theory is discussed.

Electrification of water interface.

The surface charge of a water interface determines many fundamental processes in physical chemistry and interface science, and it has been intensively studied for over a hundred years. We summarize experimental methods to characterize the surface charge densities developed so far: electrokinetics, double-layer force measurements, potentiometric titration, surface-sensitive nonlinear spectroscopy, and surface-sensitive mass spectrometry. Then, we elucidate physical ion adsorption and chemical electrification as examples of electrification mechanisms. In the end, novel effects on surface electrification are discussed in detail. We believe that this clear overview of state of the art in a charged water interface will surely help the fundamental progress of physics and chemistry at interfaces in the future.

Interfacial, Electroviscous, and Nonlinear Dielectric Effects on Electrokinetics at Highly Charged Surfaces.

The dielectric constant and the viscosity of water at the interface of hydrophilic surfaces differ from their bulk values, and it has been proposed that the deviation is caused by the strong electric field and the high ion concentration in the interfacial layer. We calculate the dependence of the dielectric constant and the viscosity of bulk electrolytes on the electric field and the salt concentration. Incorporating the concentration and field-dependent dielectric constant and viscosity in the extended Poisson-Boltzmann and Stokes equations, we calculate the electro-osmotic mobility. We compare the results to literature experimental data and explicit molecular dynamics simulations of OH-terminated surfaces and show that it is necessary to additionally include the presence of a subnanometer wide interfacial water layer, the properties of which are drastically transformed by the sheer presence of the interface. We conclude that the origin of the anomalous behavior of aqueous interfacial layers cannot be found in electrostriction or electroviscous effects caused by the interfacial electric field and ion concentration. Instead, it is primarily caused by the intrinsic ordering and orientation of the interfacial water layer.

Consistent description of ion-specificity in bulk and at interfaces by solvent implicit simulations and mean-field theory.

Solvent-implicit Monte Carlo (MC) simulations and mean-field theory are used to predict activity coefficients and excess interfacial tensions for NaF, NaCl, NaI, KF, KCl, and KI solutions in good agreement with experimental data over the entire experimentally available concentration range. The effective ionic diameters of the solvent-implicit simulation model are obtained by fits to experimental activity coefficient data. The experimental activity coefficients at high salt concentrations are only reproduced if the ion-specific concentration-dependent decrement of the dielectric constant is included. The dielectric-constant dependent contribution of the single-ion solvation free energy to the activity coefficient is significant and is included. To account for the ion-specific excess interfacial tension of salt solutions, in addition to non-ideal solution effects and the salt-concentration-dependent dielectric decrement, an ion-specific ion-interface interaction must be included. This ion-interface interaction, which acts in addition to the dielectric image-charge repulsion, is modeled as a box potential, is considerably more long-ranged than the ion radius, and is repulsive for all ions considered except iodide, in agreement with previous findings and arguments. By comparing different models that include or exclude bulk non-ideal solution behavior, dielectric decrement effects, and ion-interface interaction potentials, we demonstrate how bulk and interfacial ion-specific effects couple and partially compensate each other. Our MC simulations, which correctly include ionic correlations and interfacial dielectric image-charge repulsion, are used to determine effective ion-surface interaction potentials that can be used in a modified Poisson-Boltzmann theory.

Nanomolar Surface-Active Charged Impurities Account for the Zeta Potential of Hydrophobic Surfaces.

The electrification of hydrophobic surfaces is an intensely debated subject in physical chemistry. We theoretically study the ζ potential of hydrophobic surfaces for varying pH and salt concentration by solving the Poisson-Boltzmann and Stokes equations with individual ionic adsorption affinities. Using the ionic surface affinities extracted from the experimentally measured surface tension of the air-electrolyte interface, we first show that the interfacial adsorption and repulsion of small inorganic ions such as H3O+, OH-, HCO3-, and CO32- cannot account for the ζ potential observed in experiments because the surface affinities of these ions are too small. Even if we take hydrodynamic slip into account, the characteristic dependence of the ζ potential on pH and salt concentration cannot be reproduced. Instead, to explain the sizable experimentally measured ζ potential of hydrophobic surfaces, we assume minute amounts of impurities in the water and include the impurities' acidic and basic reactions with water. We find good agreement between our predictions and the reported experimental ζ potential data of various hydrophobic surfaces if we account for impurities that consist of a mixture of weak acids (pKa = 5-7) and weak bases (pKb = 12) at a concentration of the order of 10-7 M.

Giant Axial Dielectric Response in Water-Filled Nanotubes and Effective Electrostatic Ion-Ion Interactions from a Tensorial Dielectric Model.

Molecular dynamics simulations in conjunction with effective medium theory are used to investigate dielectric effects in water-filled nanotubes. The resulting effective axial dielectric constant shows a divergent increase for small nanotube radii that depends on the nanotube length, while the effective radial dielectric constant decreases significantly for thin nanotubes. By solving Poisson's equation for an anisotropic dielectric medium in cylindrical geometry, we show that the axial ion-ion interaction depends for small separations primarily on the radial dielectric constant, not on the axial one. This means that electrostatic ion-ion interactions in thin water-filled nanotubes are on the linear dielectric level significantly enhanced due to water confinement effects at small separations, while at large separations the outside medium dominates. If the outside medium is metallic, then the ion-ion interaction decays exponentially for large ion separation.

Crossover of the Power-Law Exponent for Carbon Nanotube Conductivity as a Function of Salinity.

On the basis of the Poisson-Boltzmann equation in cylindrical coordinates, we calculate the conductivity of a single charged nanotube filled with electrolyte. The conductivity as a function of the salt concentration follows a power-law, the exponent of which has been controversially discussed in the literature. We use the co-ion-exclusion approximation and obtain the crossover between different asymptotic power-law behaviors analytically. Numerically solving the full Poisson-Boltzmann equation, we also calculate the complete diagram of exponents as a function of the salt concentration and the pH for tubes with different radii and p Ka values. We apply our theory to recent experimental results on carbon nanotubes using the p Ka as a fit parameter. In good agreement with the experimental data, the theory shows power-law behavior with the exponents 1/3 at high pH and 1/2 at low pH, with a crossover depending on salt concentration, tube radius and p Ka.

Analytical Interfacial Layer Model for the Capacitance and Electrokinetics of Charged Aqueous Interfaces.

We construct an analytical model to account for the influence of the subnanometer-wide interfacial layer on the differential capacitance and the electro-osmotic mobility of solid-electrolyte interfaces. The interfacial layer is incorporated into the Poisson-Boltzmann and Stokes equations using a box model for the dielectric properties, the viscosity, and the ionic potential of mean force. We calculate the differential capacitance and the electro-osmotic mobility as a function of the surface charge density and the salt concentration, both with and without steric interactions between the ions. We compare the results from our theoretical model with experimental data on a variety of systems (graphite and metallic silver for capacitance and titanium oxide and silver iodide for electro-osmotic data). The differential capacitance of silver as a function of salinity and surface charge density is well reproduced by our theory, using either the width of the interfacial layer or the ionic potential of mean force as the only fitting parameter. The differential capacitance of graphite, however, needs an additional carbon capacitance to explain the experimental data. Our theory yields a power-law dependence of the electro-osmotic mobility on the surface charge density for high surface charges, reproducing the experimental data using both the interfacial parameters extracted from molecular dynamics simulations and fitted interfacial parameters. Finally, we examine different types of hydrodynamic boundary conditions for the power-law behavior of the electro-osmotic mobility, showing that a finite-viscosity layer explains the experimental data better than the usual hydrodynamic slip boundary condition. Our analytical model thus allows us to extract the properties of the subnanometer-wide interfacial layer by fitting to macroscopic experimental data.

The effects of ion adsorption on the potential of zero charge and the differential capacitance of charged aqueous interfaces.

Using a box profile approximation for the non-electrostatic surface adsorption potentials of anions and cations, we calculate the differential capacitance of aqueous electrolyte interfaces from a numerical solution of the Poisson-Boltzmann equation, including steric interactions between the ions and an inhomogeneous dielectric profile. Preferential adsorption of the positive (negative) ion shifts the minimum of the differential capacitance to positive (negative) surface potential values. The trends are similar for the potential of zero charge; however, the potential of zero charge does not correspond to the minimum of the differential capacitance in the case of asymmetric ion adsorption, contrary to the assumption commonly used to determine the potential of zero charge. Our model can be used to obtain more accurate estimates of ion adsorption properties from differential capacitance or electrocapillary measurements. Asymmetric ion adsorption also affects the relative heights of the characteristic maxima in the differential capacitance curves as a function of the surface potential, but even for strong adsorption potentials the effect is small, making it difficult to reliably determine the adsorption properties from the peak heights.

Charged Surface-Active Impurities at Nanomolar Concentration Induce Jones-Ray Effect.

The electrolyte surface tension exhibits a characteristic minimum around a salt concentration of 1 mM for all ion types, known as the Jones-Ray effect. We show that a consistent description of the experimental surface tension of salts, bases, and acids is possible by assuming charged impurities in the water with a surface affinity typical for surfactants. Comparison with experimental data yields an impurity concentration in the nanomolar range, well below the typical experimental detection limit. Our modeling reveals salt-screening enhanced impurity adsorption as the mechanism behind the Jones-Ray effect: for very low salt concentration added salt screens the  electrostatic repulsion between impurities at the surface, which dramatically increases impurity adsorption and thereby reduces the surface tension.

Interfacial layer effects on surface capacitances and electro-osmosis in electrolytes.

Many properties of the interfacial layer of water at surfaces differ significantly from those of bulk water. The consequences are most significant for the double-layer capacitance and the electrokinetic properties. We model the interfacial hydration layer by a modified dielectric constant and a modified local viscosity over a single interfacial width. Analytic expressions in the low-charge Debye-Hückel approximation are derived and shown to describe experimental surface capacitance and electro-osmotic data in a unified framework.

Nonlinear electro-osmosis of dilute non-adsorbing polymer solutions with low ionic strength.

Nonlinear electro-osmotic behaviour of dilute non-adsorbing polymer solutions with low salinity is investigated using Brownian dynamics simulations and a kinetic theory. In the Brownian simulations, the hydrodynamic interaction between the polymers and a no-slip wall is considered using the Rotne-Prager approximation of the Blake tensor. In a plug flow under a sufficiently strong applied electric field, the polymer migrates toward the bulk, forming a depletion layer thicker than the equilibrium one. Consequently, the electro-osmotic mobility increases nonlinearly with increasing electric field and becomes saturated. This nonlinear mobility does not depend qualitatively on the details of the rheological properties of the polymer solution. Analytical calculations using the kinetic theory for the same system quantitatively reproduce the results of the Brownian dynamics simulation well.

Electrophoresis of electrically neutral porous spheres induced by selective affinity of ions.

I investigate the possibility that electrically neutral porous spheres electrophorese in electrolyte solutions with asymmetric affinity of ions to spheres on the basis of electrohydrodynamics and the Poisson-Boltzmann and Debye-Bueche-Brinkman theories. Assuming a weak electric field and ignoring the double-layer polarization, I obtain analytical expressions for electrostatic potential, electrophoretic mobility, and flow field. In the equilibrium state, the Galvani potential forms across the interface of the spheres. Under a weak electric field, the spheres show finite mobility with the same sign as the Galvani potential. When the radius of the spheres is significantly larger than the Debye and hydrodynamic screening length, the mobility monotonically increases with increasing salinity.

Electro-osmotic flow of semidilute polyelectrolyte solutions.

We investigate electro-osmosis in aqueous solutions of polyelectrolytes using mean-field equations. A solution of positively charged polyelectrolytes is confined between two negatively charged planar surfaces, and an electric field is applied parallel to the surfaces. When electrostatic attraction between the polymer and the surface is strong, the polymers adhere to the surface, forming a highly viscous adsorption layer that greatly suppresses the electro-osmosis. Conversely, electro-osmosis is enhanced by depleting the polymers from the surfaces. We also found that the electro-osmotic flow is invertible when the electrostatic potential decays to its bulk value with the opposite sign. These behaviors are well explained by a simple mathematical form of the electro-osmotic coefficient.

[Survey of the preoperative smoking cessation in patients for elective surgery in a university hospital].

BACKGROUND: In 2006, we reported the smoking status of surgical patients, and the factors relating to preoperative abstinence from cigarettes. Recently implementation of smoke-free policies has increased in Japan. Therefore we performed preoperative interview of 1,124 patients scheduled for elective surgery in 2011 (during 6 months), and compared the results with those of the same interview of 1,968 patients in 2006 (during 12 months). METHODS: Anesthesiologists interviewed all patients using a standardized questionnaire regarding: medical history, smoking history, and awareness of the risks of perioperative smoking. RESULTS: Current smoking rate was not different between 2006 (7%) and 2011 (7%). It was more difficult to quit smoking preoperatively for female patients in 2011 (P = 0.030), and those with benign disease in both 2006 (P = 0.006) and 2011 (P = 0.050) [smoker vs ex-smoker (< three months)]. There was no improvement in awareness of the perioperative risk of smoking between 2006 and 2011. CONCLUSIONS: At present, the importance of perioperative smoking cessation has not been sufficiently well-known for the surgical patients. Health care workers should be more aware of the importance of informing patients that preoperative abstinence from cigarettes may decrease perioperative complications.

[A case of pulmonary artery injury which might have been caused by a pulmonary artery catheter during the mitral valve replacement].

We experienced a pulmonary artery injury which might have been caused by a pulmonary artery catheter (PAC). A 66-year-old woman after mitral valve replacement, developped massive tracheal bleeding during weaning from the cardiopulmonary bypass. Transesophageal echocardiography revealed the air bell in the right pulmonary artery synchronized with ventilation. We speculated pulmonary artery injury and performed pulmonary artery angiography; however, it could not clarify the bleeding point. Surgical approach found the air leak from the erasure of the bronchus intermedius and the lobectomy led to lifesaving. A pulmonary artery injury caused by PAC is very rare, but life-threatening. In this case, she had some risk factors (i. e. 60 years or older, female, short statue, and mitral valve disease); however, it was hard to predict the pulmonary injury from these factors.

Effects of strongly selective additives on volume phase transition in gels.

We investigate volume phase transition in gels immersed in mixture solvents, on the basis of a three-component Flory-Rehner theory. When the selectivity of the minority solvent component to the polymer network is strong, the gel tends to shrink with an increasing concentration of the additive, regardless of whether it is good or poor. This behavior originates from the difference of the additive concentration between inside and outside the gel. We also found the gap of the gel volume at the transition point can be controlled by adding the strongly selective solutes. By dissolving a strongly poor additive, for instance, the discontinuous volume phase transition can be extinguished. Furthermore, we observed that another volume phase transition occurs far from the original transition point. These behaviors can be well explained by a simplified theory neglecting the nonlinearity of the additive concentration.

[Alteration of cerebral blood flow by modified electroconvulsive therapy in major depression].

BACKGROUND: Modified electroconvulsive therapy (mECT) aims to improve major depression, giving an electronic stimulation to a patient in order to make tonic-clonic convulsion. Elevation of regional cerebral oxygen saturation (rSO2) was reported just after stimulation. Increase of oxygen consumption in brain is compensated by increase of cerebral blood flow. Oxygenation and blood flow over the entire brain are evaluated by measuring rSO2 at forehead. We followed alteration of rSO2 at each mECT. METHODS: rSO2 was measured by INVOS 5100 (Edwards Lifesciences). Patients had Somasensor placed at the right and left forehead, rSO2 was measured from before and after mECT. After general anesthesia induction, patients were stimulated by Tymatron SYSTEM IV (Somatics, America). Intensity of stimulation was decided by a single psychiatrist. We showed rSO2 values as follows: before stimulation (before), minimum value after stimulation (mini) and maximum value after stimulation (max). Hamilton depression scale (HAM-D) was used for severity of depression. RESULTS: All patients showed improved HAM-D. The values of (max-before)/before of rSO2 increased at the end of the therapy. CONCLUSIONS: We suggested that the response of cerebral vasculatures for electroconvulsive stimulation was improved as depression was improved.