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

Thermodynamics of nano-cluster phases: a unifying theory

We propose a unifying, analytical theory accounting for the self-organization of colloidal systems in nano- or micro-cluster phases. We predict the distribution of cluter sizes with respect to interaction parameters and colloid concentration. In particular, we anticipate a proportionality regime where the mean cluster size grows proportionally to the concentration, as observed in several experiments. We emphasize the interest of a predictive theory in soft matter, nano-technologies and biophysics.Comment: 4 pages, 1 figur

Minimal Bending Energies of Bilayer Polyhedra

Motivated by recent experiments on bilayer polyhedra composed of amphiphilic molecules, we study the elastic bending energies of bilayer vesicles forming polyhedral shapes. Allowing for segregation of excess amphiphiles along the ridges of polyhedra, we find that bilayer polyhedra can indeed have lower bending energies than spherical bilayer vesicles. However, our analysis also implies that, contrary to what has been suggested on the basis of experiments, the snub dodecahedron, rather than the icosahedron, generally represents the energetically favorable shape of bilayer polyhedra

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

Universal reduction of pressure between charged surfaces by long-wavelength surface charge modulation

We predict theoretically that long-wavelength surface charge modulations universally reduce the pressure between the charged surfaces with counterions compared with the case of uniformly charged surfaces with the same average surface charge density. The physical origin of this effect is the fact that surface charge modulations always lead to enhanced counterion localization near the surfaces, and hence, fewer charges at the midplane. We confirm the last prediction with Monte Carlo simulations.Comment: 8 pages 1 figure, Europhys. Lett., in pres

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

Signal Traits and Oxidative Stress: A Comparative Study across Populations with Divergent Signals

Diverging populations often shift patterns of signal use – a process that can contribute to reproductive isolation and speciation. Yet it is not clear why most traits gain or lose signal value during divergence. One reason this could occur is because changes in the relationship between signals and relevant physiological parameters degrade the reliability of a signal, or even change its underlying information content. Here we test the hypothesis that the relationship between signal trait elaboration and a central component of organismal health – oxidative stress – differs across closely related populations that have diverged in signal use and preferences. In the recently diverged barn swallow subspecies complex (Hirundo rustica, Family: Hirundinidae), different populations use different traits as sexual signals. Two of these traits, ventral breast plumage color and tail streamer length, differ markedly between North American H. r. erythrogaster and European H. r. rustica. Despite this divergence, variation in ventral plumage color was similarly associated with measures of oxidative damage across both populations. However, the directionality of these relationships differed between the sexes: darker male barn swallows had higher levels of plasma oxidative damage than their lighter counterparts, while the opposite relationship was seen in females. In contrast, relationships between tail streamer length and measures of oxidative stress were not consistent across populations. Some analyses indicated that in European H. r. rustica, where males bearing elongated streamers are preferred as mates, longer-streamered males were more oxidatively stressed; however, the opposite pattern was suggested in North American H. r. erythrogaster. Tail streamer length was not associated with measures of oxidative stress in females of either population. Differences in the physiological state of stronger signalers across populations and between the sexes may be related to costs or constraints on signal elaboration (e.g., biochemical pathways associated with melanogenesis), or reflect differences in how signal-mediated social interactions influence oxidative stress. Overall, our results suggest that while some phenotypic traits appear to be capable of conveying similar physiological information regardless of their use as signals, divergence in other phenotypic traits may be associated with shifts in their information content

Signal Traits and Oxidative Stress: A Comparative Study across Populations with Divergent Signals

Diverging populations often shift patterns of signal use – a process that can contribute to reproductive isolation and speciation. Yet it is not clear why most traits gain or lose signal value during divergence. One reason this could occur is because changes in the relationship between signals and relevant physiological parameters degrade the reliability of a signal, or even change its underlying information content. Here we test the hypothesis that the relationship between signal trait elaboration and a central component of organismal health – oxidative stress – differs across closely related populations that have diverged in signal use and preferences. In the recently diverged barn swallow subspecies complex (Hirundo rustica, Family: Hirundinidae), different populations use different traits as sexual signals. Two of these traits, ventral breast plumage color and tail streamer length, differ markedly between North American H. r. erythrogaster and European H. r. rustica. Despite this divergence, variation in ventral plumage color was similarly associated with measures of oxidative damage across both populations. However, the directionality of these relationships differed between the sexes: darker male barn swallows had higher levels of plasma oxidative damage than their lighter counterparts, while the opposite relationship was seen in females. In contrast, relationships between tail streamer length and measures of oxidative stress were not consistent across populations. Some analyses indicated that in European H. r. rustica, where males bearing elongated streamers are preferred as mates, longer-streamered males were more oxidatively stressed; however, the opposite pattern was suggested in North American H. r. erythrogaster. Tail streamer length was not associated with measures of oxidative stress in females of either population. Differences in the physiological state of stronger signalers across populations and between the sexes may be related to costs or constraints on signal elaboration (e.g., biochemical pathways associated with melanogenesis), or reflect differences in how signal-mediated social interactions influence oxidative stress. Overall, our results suggest that while some phenotypic traits appear to be capable of conveying similar physiological information regardless of their use as signals, divergence in other phenotypic traits may be associated with shifts in their information content