We examine the effective force between two nanometer scale solutes in water by Molecular Dynamics simulations. Macroscopic considerations predict a strong reduction of the hydrophobic attraction between solutes when the latter are charged. This is confirmed by the simulations which point to a surprising constancy of the effective force between oppositely charged solutes at contact, while like charged solutes lead to significantly different behavior between positive and negative pairs. The latter exhibit the phenomenon of ``like-charge attraction" previously observed in some colloidal dispersions.Comment: 4 pages, 5 figure

We use thermodynamic perturbation theory to calculate the free energies and resulting phase diagrams of binary systems of spherical colloidal particles and interacting polymer coils in good solvent within an effective one-component representation of such mixtures, whereby the colloidal particles interact via a polymer-induced depletion potential. MC simulations are used to test the convergence of the high temperature expansion of the free energy. The phase diagrams calculated for several polymer to colloid size ratios differ considerably from the results of similar calculations for mixtures of colloids and ideal (non-interacting) polymers, and are in good overall agreement with the results of an explicit two-component representation of the same system, which includes more than two-body depletion forces.

Water at normal conditions is a fluid thermodynamically close to the liquid-vapor phase coexistence and features a large surface tension. This combination can lead to interesting capillary phenomena on microscopic scales. Explicitwater molecular dynamics (MD) computer simulations of hydrophobic solutes, for instance, give evidence of capillary evaporation on nanometer scales, i.e., the formation of nanometer-sized vapor bubbles (nanobubbles) between confining hydrophobic surfaces. This phenomenon has been exemplified for solutes with varying complexity, e.g., paraffin plates, coarse-grained homopolymers, biological and solid-state channels, and atomistically resolved proteins. It has been argued that nanobubbles strongly impact interactions in nanofluidic devices, translocation processes, and even in protein stability, function, and folding. As large-scale MD simulations are computationally expensive, the efficient multiscale modeling of nanobubbles and the prediction of their stability poses a formidable task to the 'nanophysical' community. Recently, we have presented a conceptually novel and versatile implicit solvent model, namely, the variational implicit solvent model (VISM), which is based on a geometric energy functional. As reviewed here, first solvation studies of simple hydrophobic solutes using VISM coupled with the numerical level-set scheme show promising results, and, in particular, capture nanobubble formation and its subtle competition to local energetic potentials in hydrophobic confinement.

Recent results in theory and simulation of star-polymer-colloid mixtures are reviewed. We present the effective interaction between hard, colloidal particles and star polymers in a good solvent derived by monomer-resolved Molecular Dynamics simulations and theoretical arguments. The relevant parameters are the size ratio q between the stars and the colloids, as well as the number of polymeric arms f (functionality) attached to the common center of the star. By covering a wide range of q 's ranging from zero (star against a flat wall) up to about 0.5, we establish analytical forms for the star-colloid interaction which are in excellent agreement with simulation results. By employing this cross interaction and the effective interactions between stars and colloids themselves, a demixing transition in the fluid phase is observed and systematically investigated for different arm numbers and size ratios. The demixing binodals are compared with experimental observations and found to be consistent. Furthermore, we map the full two-component system on an effective one-component description for the colloids, by inverting the two-component Ornstein-Zernike equations. Some recent results for the depletion interaction and freezing transitions are shown.