Surface-induced layer formation in polyelectrolytes

We analyze, by means of an RPA calculation, the conditions under which a mixture of oppositely charged polyelectrolytes can micro-segregate in the neighborhood of a charged surface creating a layered structure. A number of stable layers can be formed if the surface is sufficiently strongly charged even at temperatures at which the bulk of the mixture is homogeneous.Comment: 6 pages, 3 figures, revtex, epsf, psfi

Competing Interactions among Supramolecular Structures on Surfaces

A simple model was constructed to describe the polar ordering of non-centrosymmetric supramolecular aggregates formed by self assembling triblock rodcoil polymers. The aggregates are modeled as dipoles in a lattice with an Ising-like penalty associated with reversing the orientation of nearest neighbor dipoles. The choice of the potentials is based on experimental results and structural features of the supramolecular objects. For films of finite thickness, we find a periodic structure along an arbitrary direction perpendicular to the substrate normal, where the repeat unit is composed of two equal width domains with dipole up and dipole down configuration. When a short range interaction between the surface and the dipoles is included the balance between the up and down dipole domains is broken. Our results suggest that due to surface effects, films of finite thickness have a none zero macroscopic polarization, and that the polarization per unit volume appears to be a function of film thickness.Comment: 3 pages, 3 eps figure

Competing interactions in two dimensional Coulomb systems: Surface charge heterogeneities in co-assembled cationic-anionic incompatible mixtures

A binary mixture of oppositely charged components confined to a plane such as cationic and anionic lipid bilayers may exhibit local segregation. The relative strength of the net short range interactions, which favors macroscopic segregation, and the long range electrostatic interactions, which favors mixing, determines the length scale of the finite size or microphase segregation. The free energy of the system can be examined analytically in two separate regimes, when considering small density fluctuations at high temperatures, and when considering the periodic ordering of the system at low temperatures (F. J. Solis and M. Olvera de la Cruz, J. Chem. Phys. 122, 054905 (2000)). A simple Molecular Dynamics simulation of oppositely charged monomers, interacting with a short range Lennard Jones potential and confined to a two dimensional plane, is examined at different strengths of short and long range interactions. The system exhibits well-defined domains that can be characterized by their periodic length-scale as well as the orientational ordering of their interfaces. By adding salt, the ordering of the domains disappears and the mixture macroscopically phase segregates in agreement with analytical predictions.Comment: 8 pages, 5 figures, accepted for publication in J. Chem. Phys, Figure 1 include

Spontaneous chirality via long-range electrostatic forces

We consider a model for periodic patterns of charges constrained over a cylindrical surface. In particular we focus on patterns of chiral helices, achiral rings or vertical lamellae, with the constraint of global electroneutrality. We study the dependence of the patterns' size and pitch angle on the radius of the cylinder and salt concentration. We obtain a phase diagram by using numerical and analytic techniques. For pure Coulomb interactions, we find a ring phase for small radii and a chiral helical phase for large radii. At a critical salt concentration, the characteristic domain size diverges, resulting in macroscopic phase segregation of the components and restoring chiral symmetry. We discuss possible consequences and generalizations of our model.Comment: Revtex, 4 pages, 4 figure

Hydrodynamics of thermally-driven chiral propulsion and separation

Considerable effort has been directed towards the characterization of chiral mesoscale structures, as shown in chiral protein assemblies and carbon nanotubes. Here, we establish a thermally-driven hydrodynamic description for the actuation and separation of mesoscale chiral structures in a fluid medium. Cross flow of a Newtonian liquid with a thermal gradient gives rise to chiral structure propulsion and separation according to their handedness. In turn, the chiral suspension alters the liquid flow which thus acquires a transverse (chiral) velocity component. Since observation of the predicted effects requires a low degree of sophistication, our work provides an efficient and inexpensive approach to test and calibrate chiral particle propulsion and separation strategies

Charged Particles on Surfaces: Coexistence of Dilute Phases and Periodic Structures on Membranes

We consider a mixture of one neutral and two oppositely charged types of molecules confined to a surface. Using analytical techniques and molecular dynamics simulations, we construct the phase diagram of the system and exhibit the coexistence between a patterned solid phase and a charge-dilute phase. The patterns in the solid phase arise from competition between short-range immiscibility and long-range electrostatic attractions between the charged species. The coexistence between phases leads to observations of stable patterned domains immersed in a neutral matrix background.Comment: 5 pages, 3 figure

Electrostatic attraction between cationic-anionic assemblies with surface compositional heterogeneities

Electrostatics plays a key role in biomolecular assembly. Oppositely charged biomolecules, for instance, can co-assembled into functional units, such as DNA and histone proteins into nucleosomes and actin-binding protein complexes into cytoskeleton components, at appropriate ionic conditions. These cationic-anionic co-assemblies often have surface charge heterogeneities that result from the delicate balance between electrostatics and packing constraints. Despite their importance, the precise role of surface charge heterogeneities in the organization of cationic-anionic co-assemblies is not well understood. We show here that co-assemblies with charge heterogeneities strongly interact through polarization of the domains. We find that this leads to symmetry breaking, which is important for functional capabilities, and structural changes, which is crucial in the organization of co-assemblies. We determine the range and strength of the attraction as a function of the competition between the steric and hydrophobic constraints and electrostatic interactions.Comment: JCP June/200