Soft matter materials, such as polymers, membranes, proteins, are often electrically charged. This makes them water soluble, which is of great importance in technological application and a prerequisite for biological function. We discuss a few static and dynamic systems that are dominated by charge effects. One class comprises complexation between oppositely charged objects, for example the adsorption of charged ions or charged polymers on oppositely charged substrates of different geometry. Here the main questions are whether adsorption occurs and what the effective charge of the resulting complex is. We explicitly discuss the adsorption behavior of polyelectrolytes on substrates of planar, cylindrical and spherical geometry with specific reference to DNA adsorption on supported charged lipid layers, DNA adsorption on oppositely charged cylindrical dendro-polymers, and DNA binding on globular histone proteins, respectively. In all these systems salt plays an important role, and some of the important features can already be obtained on the linear Debye-Hückel level. The second class comprises effective interactions between similarly charged objects. Here the main theme is to understand the experimental finding that similarly and highly charged bodies attract each other in the presence of multi-valent counterions. This is demonstrated using field-theoretic arguments as well as Monte-Carlo simulations for the case of two homogeneously charged bodies. Realistic surfaces, on the other hand, are corrugated and also exhibit modulated charge distributions, which is important for static properties such as the counterion-density distribution, but has even more pronounced consequences for dynamic properties such as the counterion mobility. More pronounced dynamic effects are obtained with highly condensed charged systems in strong electric fields. Likewise, an electrostatically collapsed highly charged polymer is unfolded and oriented in strong electric fields. All charged systems occur in water, and water by itself is not a very well understood material. At the end of this review, we give a very brief and incomplete account of the behavior of water at planar surfaces. The coupling between water structure and charge effects is largely unexplored, and a few directions for future research are sketched. On an even more nanoscopic level, we demonstrate using ab-initio methods that specific interactions between oppositely charged groups (which occur when their electron orbitals start to overlap) are important and cause ion-specific effects that have recently moved into the focus of interest.

Charged soft-matter systems-such as colloidal dispersions and charged polymers-are dominated by attractive forces between constituent like-charged particles when neutralizing counterions of high charge valency are introduced. Such counter-intuitive effects indicate strong electrostatic coupling between like-charged particles, which essentially results from electrostatic correlations among counterions residing near particle surfaces. In this paper, the attraction mechanism and the structure of counterionic correlations are discussed in the limit of strong coupling based on recent numerical and analytical investigations and for various geometries (planar, spherical and cylindrical) of charged objects.

We present a personal view on the current state of statistical mechanics of Coulomb fluids with special emphasis on the interactions between macromolecular surfaces, concentrating on the weak and the strong coupling limits. Both are introduced for a (primitive) counterion-only system in the presence of macroscopic, uniformly charged boundaries, where they can be derived systematically. Later we show how this formalism can be generalized to the cases with additional characteristic length scales that introduce new coupling parameters into the problem. These cases most notably include asymmetric ionic mixtures with mono-and multivalent ions that couple differently to charged surfaces, ions with internal charge (multipolar) structure and finite static polarizability, where weak and strong coupling limits can be constructed by analogy with the counterion-only case and lead to important new insights into their properties that cannot be derived by any other means. © 2013 AIP Publishing LLC. [http://dx

We reformulate the theory of strong electrostatic coupling in order to describe an asymmetric electrolyte solution of monovalent salt ions and polyvalent counterions using field-theoretical techniques and Monte Carlo simulations. The theory is based on an asymmetric treatment of the different components of the electrolyte solution. The weak coupling Debye-Hückel approach is used in order to describe the monovalent salt ions while a strong coupling approach is used to tackle the polyvalent counterions. This combined weak-strong coupling approach effectively leads to dressed interactions between polyvalent counterions and thus directly affects the correlation attraction mediated by polyvalent counterions between like-charged objects. The general theory is specifically applied to a system composed of two uniformly charged plane-parallel surfaces in the presence of salt and polyvalent counterions. In the strong coupling limit for polyvalent counterions, the comparison with Monte Carlo simulations shows good agreement for large enough values of the electrostatic coupling parameter. We delineate two limiting laws that in fact encompass all the Monte Carlo data.

We investigate the ion distribution and overcharging at charged interfaces with dielectric inhomogeneities in the presence of asymmetric electrolytes containing polyvalent and monovalent ions. We formulate an effective "dressed counterion" approach by integrating out the monovalent salt degrees of freedom and show that it agrees with results of explicit Monte-Carlo simulations. We then apply the dressed counterion approach within the framework of the strong-coupling theory, valid for polyvalent ions at low concentrations, which enables an analytical description for salt effects as well as dielectric inhomogeneities in the limit of strong Coulomb interactions on a systematic level. Limitations and applicability of this theory are examined by comparing the results with simulations.

Abstract. Like-charged macroions attract each other as a result of strong electrostatic correlations in the presence of multivalent counterions or at low temperatures. We investigate the effective electrostatic interaction between i) two like-charged rods and ii) two like-charged spheres using the recently introduced strong-coupling theory, which becomes asymptotically exact in the limit of large coupling parameter (i.e. for large counterion valency, low temperature, or high surface charge density on macroions). In contrast to previous applications of the strong-coupling theory, we deal with curved surfaces and an additional parameter, referred to as Manning parameter, is introduced, which measures the ratio between the radius of curvature of macroions to the Gouy-Chapman length. This parameter, together with the size of the confining box enclosing the two macroions and their neutralizing counterions, controls the counterion-condensation process that directly affects the effective interactions. For sufficiently large Manning parameters (weakly-curved surfaces), we find a strong long-ranged attraction between two macroions that form a closely-packed bound state with small surface-to-surface separation of the order of the counterion diameter in agreement with recent simulations results. For small Manning parameters (highly-curved surfaces), on the other hand, the equilibrium separation increases and the macroions unbind from each other as the confinement volume increases to infinity. This occurs via a continuous universal unbinding transition for two charged rods at a threshold Manning parameter of ξc = 2/3, while the transition is strongly discontinuous for spheres because of a pronounced potential barrier at intermediate distances. Unlike the cylindrical case, the attractive forces between spheres disappear for increasing confinement volume due to the complete de-condensation of counterions. Scaling arguments suggest that for moderate values of coupling parameter, strong-coupling predictions remain valid for sufficiently small surface-to-surface separations.PACS. 87.15.-v Biomolecules: structure and physical properties -82.70.Dd Colloids -87.15.Nn Properties of solutions; aggregation and crystallization of macromolecules

Counterions at charged rod-like polymers exhibit a condensation transition at a critical temperature (or equivalently, at a critical linear charge density for polymers), which dramatically influences various static and dynamic properties of charged polymers. We address the critical and universal aspects of this transition for counterions at a single charged cylinder in both two and three spatial dimensions using numerical and analytical methods. By introducing a novel Monte-Carlo sampling method in logarithmic radial scale, we are able to numerically simulate the critical limit of infinite system size (corresponding to infinite-dilution limit) within tractable equilibration times. The critical exponents are determined for the inverse moments of the counterionic density profile (which play the role of the order parameters and represent the inverse localization length of counterions) both within mean-field theory and within Monte-Carlo simulations. In three dimensions, we demonstrate that correlation effects (neglected within mean-field theory) lead to an excessive accumulation of counterions near the charged cylinder below the critical temperature (condensation phase), while surprisingly, the critical region exhibits universal critical exponents in accord with the mean-field theory. Also in contrast with the typical trend in bulk critical phenomena, where fluctuations are strongly enhanced in lower dimensions, we demonstrate, using both numerical and analytical approaches, that the mean-field theory becomes exact for the 2D counterion-cylinder system at all temperatures (Manning parameters), when number of counterions tends to infinity. For finite particle number, however, the 2D problem displays a series of peculiar singular points (with diverging heat capacity), which reflect successive de-localization events of individual counterions from the central cylinder. In both 2D and 3D, the heat capacity shows a universal jump at the critical point, and the energy develops a pronounced peak. The asymptotic behavior of the energy peak location is used to locate the critical point, which is also found to be universal and in accordance with the mean-field prediction.

We investigate polyelectrolyte brushes in the osmotic regime using both theoretical analysis and molecular dynamics simulation techniques. In the simulations at moderate Bjerrum length, we observe that the brush height varies weakly with grafting density, in contrast to the accepted scaling law, which predicts a brush thickness independent of the grafting density. We show that such behavior can be explained by considering lateral electrostatic effects (within the non-linear Poisson-Boltzmann theory) combined with the coupling between lateral and longitudinal degrees of freedom due to the conserved polymer volume (which are neglected in scaling arguments). We also take the non-linear elasticity of polyelectrolyte chains into consideration, which makes significant effects as chains are almost fully stretched in the osmotic regime. It is shown that all these factors lead to a non-monotonic behavior for the brush height as a function of the grafting density. At large grafting densities, the brush height increases with increasing the grafting density due to the volume constraint. At small grafting densities, we obtain a re-stretching of the chains for decreasing grafting density, which is caused by lateral electrostatic contributions and is controlled by the counterion-condensation process around polyelectrolyte chains. These results are obtained assuming all counterions to be trapped within the brush, which is valid for sufficiently long chains of large charge fraction.