Surface tension of electrolytes: Hydrophilic and hydrophobic ions near an interface

We calculate the ion distributions around an interface in fluid mixtures of highly polar and less polar fluids (water and oil) for two and three ion species. We take into account the solvation and image interactions between ions and solvent. We show that hydrophilic and hydrophobic ions tend to undergo a microphase separation at an interface, giving rise to an enlarged electric double layer. We also derive a general expression for the surface tension of electrolyte systems, which contains a negative electrostatic contribution proportional to the square root of the bulk salt density. The amplitude of this square-root term is small for hydrophilic ion pairs, but is much increased for hydrophilic and hydrophobic ion pairs. For three ion species including hydrophilic and hydrophobic ions, we calculate the ion distributions to explain those obtained by x-ray reflectivity measurements.Comment: 8 figure

Are stress-free membranes really 'tensionless'?

In recent years it has been argued that the tension parameter driving the fluctuations of fluid membranes, differs from the imposed lateral stress, the 'frame tension'. In particular, stress-free membranes were predicted to have a residual fluctuation tension. In the present paper, this argument is reconsidered and shown to be inherently inconsistent -- in the sense that a linearized theory, the Monge model, is used to predict a nonlinear effect. Furthermore, numerical simulations of one-dimensional stiff membranes are presented which clearly demonstrate, first, that the internal 'intrinsic' stress in membranes indeed differs from the frame tension as conjectured, but second, that the fluctuations are nevertheless driven by the frame tension. With this assumption, the predictions of the Monge model agree excellently with the simulation data for stiffness and tension values spanning several orders of magnitude

Effect of dipolar moments in domain sizes of lipid bilayers and monolayers

Lipid domains are found in systems such as multi-component bilayer membranes and single component monolayers at the air-water interface. It was shown by Andelman et al. (Comptes Rendus 301, 675 (1985)) and McConnell et al. (Phys. Chem. {\bf 91}, 6417 (1987)) that in monolayers, the size of the domains results from balancing the line tension, which favors the formation of a large single circular domain, against the electrostatic cost of assembling the dipolar moments of the lipids. In this paper, we present an exact analytical expression for the electric potential, ion distribution and electrostatic free energy for different problems consisting of three different slabs with different dielectric constants and Debye lengths, with a circular homogeneous dipolar density in the middle slab. From these solutions, we extend the calculation of domain sizes for monolayers to include the effects of finite ionic strength, dielectric discontinuities (or image charges) and the polarizability of the dipoles and further generalize the calculations to account for domains in lipid bilayers. In monolayers, the size of the domains is dependent on the different dielectric constants but independent of ionic strength. In asymmetric bilayers, where the inner and outer leaflets have different dipolar densities, domains show a strong size dependence with ionic strength, with molecular-sized domains that grow to macroscopic phase separation with increasing ionic strength. We discuss the implications of the results for experiments and briefly consider their relation to other two dimensional systems such as Wigner crystals or heteroepitaxial growth.Comment: 13 pages, 5 figues in eps Replaced with new version, one citation added and a few statements corrected. The results of the paper are unchange

Membrane fluctuations near a plane rigid surface

We use analytical calculations and Monte Carlo simulations to determine the thermal fluctuation spectrum of a membrane patch of a few tens of nanometer in size, whose corners are located at a fixed distance $d$ above a plane rigid surface. Our analysis shows that the surface influence on the bilayer fluctuations can be effectively described in terms of a uniform confining potential that grows quadratically with the height of the membrane $h$ relative to the surface: $V=(1/2)\gamma h^2$. The strength $\gamma$ of the harmonic confining potential vanishes when the corners of the membrane patch are placed directly on the surface ($d=0$), and achieves its maximum value when $d$ is of the order of a few nanometers. However, even at maximum strength the confinement effect is quite small and has noticeable impact only on the amplitude of the largest bending mode.Comment: Accepted for publication in Phys. Rev.

Surface tension in bilayer membranes with fixed projected area

We study the elastic response of bilayer membranes with fixed projected area to both stretching and shape deformations. A surface tension is associated to each of these deformations. By using model amphiphilic membranes and computer simulations, we are able to observe both the types of deformation, and thus, both the surface tensions, related to each type of deformation, are measured for the same system. These surface tensions are found to assume different values in the same bilayer membrane: in particular they vanish for different values of the projected area. We introduce a simple theory which relates the two quantities and successfully apply it to the data obtained with computer simulations

Electrostatic Interactions of Asymmetrically Charged Membranes

We predict the nature (attractive or repulsive) and range (exponentially screened or long-range power law) of the electrostatic interactions of oppositely charged and planar plates as a function of the salt concentration and surface charge densities (whose absolute magnitudes are not necessarily equal). An analytical expression for the crossover between attractive and repulsive pressure is obtained as a function of the salt concentration. This condition reduces to the high-salt limit of Parsegian and Gingell where the interaction is exponentially screened and to the zero salt limit of Lau and Pincus in which the important length scales are the inter-plate separation and the Gouy-Chapman length. In the regime of low salt and high surface charges we predict - for any ratio of the charges on the surfaces - that the attractive pressure is long-ranged as a function of the spacing. The attractive pressure is related to the decrease in counter-ion concentration as the inter-plate distance is decreased. Our theory predicts several scaling regimes with different scaling expressions for the pressure as function of salinity and surface charge densities. The pressure predictions can be related to surface force experiments of oppositely charged surfaces that are prepared by coating one of the mica surfaces with an oppositely charged polyelectrolyte

The lamellar-to-isotropic transition in ternary amphiphilic systems

We study the dependence of the phase behavior of ternary amphiphilic systems on composition and temperature. Our analysis is based on a curvature elastic model of the surfactant film with sufficiently large spontaneous curvature and sufficiently negative saddle-splay modulus that the stable phases are the lamellar phase and a droplet microemulsion. In addition to the curvature energy, we consider the contributions to the free energy of the long-ranged van der Waals interaction and of the undulation modes. We find that for bending rigidities of order k_B T, the lamellar phase extends further and further into the water apex of the phase diagram as the phase inversion temperature is approached, in good agreement with experimental results.Comment: LaTeX2e, 11 pages with references and 2 eps figures included, submitted to Europhys. Let

Co-evolution of plumage characteristics and winter sociality in New and Old World sparrows

Understanding the evolution of phenotypic diversity, including the stunning array of avian plumage characters, is a central goal of evolutionary biology. Here, we applied a comparative analysis to test factors associated with the origin and maintenance of black chest and throat patches, which in some taxa are referred to as ‘badges-of-status’. Specifically, we tested whether the evolution of black colour patches in Old and New World sparrows is consistent with a signalling function during the nonbreeding season or breeding season. We found no positive associations between patch evolution and polygyny or summer sociality. Instead, patch evolution is significantly associated with sociality during the nonbreeding season. Additionally, unlike typical plumage characteristics under sexual selection, these patches are visible throughout the nonbreeding season. Further, the pattern of patch dimorphism uncovered in this study does not match expectations for a trait that evolved in a reproductive context. In particular, patch dimorphism is not associated with polygyny or the presence of extra-pair mating although other types of plumage dimorphism are strongly associated with nonmonogamous mating systems. Overall, patterns of patch evolution suggest that they are more strongly associated with social competition during the nonbreeding season than sexual competition during the breeding season. These results clarify why some previous work has uncovered puzzling relationships between black plumage patches and reproductive behaviour. We discuss these findings in the context of signal theory and previous work on badges-of-status.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/78723/1/j.1420-9101.2009.01861.x.pd

Singular electrostatic energy of nanoparticle clusters

The binding of clusters of metal nanoparticles is partly electrostatic. We address difficulties in calculating the electrostatic energy when high charging energies limit the total charge to a single quantum, entailing unequal potentials on the particles. We show that the energy at small separation $h$ has a strong logarithmic dependence on $h$. We give a general law for the strength of this logarithmic correction in terms of a) the energy at contact ignoring the charge quantization effects and b) an adjacency matrix specifying which spheres of the cluster are in contact and which is charged. We verify the theory by comparing the predicted energies for a tetrahedral cluster with an explicit numerical calculation.Comment: 17 pages, 3 figures. Submitted to Phys Rev

Saddle-splay modulus of a particle-laden fluid interface

The scaled-particle theory equation of state for the two-dimensional hard-disk fluid on a curved surface is proposed and used to determine the saddle-splay modulus of a particle-laden fluid interface. The resulting contribution to saddle-splay modulus, which is caused by thermal motion of the adsorbed particles, is comparable in magnitude with the saddle-splay modulus of a simple fluid interface.Comment: 10 pages, 2 figure