Direct Observation of Confinement-Induced Charge Inversion at a Metal Surface.

Surface interactions across water are central to areas from nanomedicine to colloidal stability. They are predominantly a combination of attractive but short-ranged dispersive (van der Waals) forces, and long-ranged electrostatic forces between the charged surfaces. Here we show, using a surface force balance, that electrostatic forces between two surfaces across water, one at constant charge while the other (a molecularly smooth metal surface) is at constant potential of the same sign, may revert smoothly from repulsion to attraction on progressive confinement of the aqueous intersurface gap.

Response of adherent cells to mechanical perturbations of the surrounding matrix.

We present a generic and unified theory to explain how cells respond to perturbations of their mechanical environment such as the presence of neighboring cells, slowly applied stretch, or gradients of matrix rigidity. Motivated by experiments, we calculate the local balance of forces that give rise to a tendency for the cell to locally move or reorient, with a focus on the contribution of feedback and homeostasis to cell contractility (manifested by a fixed displacement, strain or stress) that acts on the adhesions at the cell boundary. These forces can be either reinforced or diminished by elastic stresses due to mechanical perturbations of the matrix.

Interaction between heterogeneously charged surfaces: surface patches and charge modulation.

When solid surfaces are immersed in aqueous solutions, some of their charges can dissociate and leave behind charged patches on the surface. Although the charges are distributed heterogeneously on the surface, most of the theoretical models treat them as homogeneous. For overall non-neutral surfaces, the assumption of surface charge homogeneity is rather reasonable since the leading terms of two such interacting surfaces depend on the nonzero average charge.

Long-ranged attraction between disordered heterogeneous surfaces.

Interactions in aqueous media between uniformly charged surfaces are well understood, but most real surfaces are heterogeneous and disordered. Here we show that two such heterogeneous surfaces covered with random charge domains experience a long-range attraction across water that is orders of magnitude stronger than van der Waals forces, even in the complete absence of any charge correlations between the opposing surfaces. We demonstrate that such strong attraction may arise generally, even for overall neutral surfaces, from the inherent interaction asymmetry between equally and between oppositely charged domains.

Dielectric decrement as a source of ion-specific effects.

Many theoretical studies were devoted in the past to ion-specific effects trying to interpret a large body of experimental evidence, such as surface tension at air/water interfaces and force measurements between charged objects. Although several mechanisms were suggested to explain the results, such as dispersion forces and specific surface-ion interactions, we would like to suggest another source of ion-specificity originating from the local variations of the dielectric constant due to the presence of ions in the solution. We present a mean-field model to account for the heterogeneity of the dielectric constant caused by the ions.

Beyond standard Poisson-Boltzmann theory: ion-specific interactions in aqueous solutions.

The Poisson-Boltzmann mean-field description of ionic solutions has been successfully used in predicting charge distributions and interactions between charged macromolecules. While the electrostatic model of charged fluids, on which the Poisson-Boltzmann description rests, and its statistical mechanical consequences have been scrutinized in great detail, much less is understood about its probable shortcomings when dealing with various aspects of real physical, chemical and biological systems. These shortcomings are not only a consequence of the limitations of the mean-field approximation per se, but perhaps are primarily due to the fact that the purely Coulombic model Hamiltonian does not take into account various additional interactions that are not electrostatic in their origin.

Direct measurement of sub-Debye-length attraction between oppositely charged surfaces.

Using a surface force balance with fast video analysis, we have measured directly the attractive forces between oppositely charged solid surfaces (charge densities sigma(+), sigma(-)) across water over the entire range of interaction, in particular, at surface separations D below the Debye screening length lambda(S). At very low salt concentration we find a long-ranged attraction between the surfaces (onset ca. 100 nm), whose variation at D View Article and Find Full Text PDF

Ions in mixed dielectric solvents: density profiles and osmotic pressure between charged interfaces.

The forces between charged macromolecules, usually given in terms of osmotic pressure, are highly affected by the intervening ionic solution. While in most theoretical studies the solution is treated as a homogeneous structureless dielectric medium, recent experimental studies concluded that, for a bathing solution composed of two solvents (binary mixture), the osmotic pressure between charged macromolecules is affected by the binary solvent composition. By adding local solvent composition terms to the free energy, we obtain a general expression for the osmotic pressure, in planar geometry and within the mean-field framework.