Effect of Adsorbing and Nonadsorbing Polymer on the Interaction Between Colloidal Particles

In this paper it is described how a recent theoretical model can be applied to a system of two colloidal particles in the presence of adsorbing and nonadsorbing polymer. It turns out that in the case of adsorption the most suitable boundary condition is restricted equilibrium, in which a constant amount of polymer is in local equilibrium inside the gap between two particles. At a low polymer dose the formation of bridges gives rise to bridging flocculation, at higher amounts of polymer steric stabilization occurs due to the mutual repulsion of two extended polymer layers. If the polymer does not adsorb on the particles, full equilibrium applies in which the chemical potentials of solvent and polymer in the gap are the same as in the equilibrium bulk solution, The depletion of polymer near the surface may lead to depletion flocculation in not too concentrated polymer solutions. In very concentrated systems the thickness of the depletion zone is relatively small, and the attraction between the particles becomes too weak to overcome the particle entropy, Then the system is restabilized

Entropy-induced smectic phases in rod-coil copolymers

We present a self-consistent field theory (SCFT) of semiflexible (wormlike) diblock copolymers, each consisting of a rigid and a flexible part. The segments of the polymers are otherwise identical, in particular with regard to their interactions, which are taken to be of an Onsager excluded-volume type. The theory is developed in a general three-dimensional form, as well as in a simpler one-dimensional version. Using the latter, we demonstrate that the theory predicts the formation of a partial-bilayer smectic-A phase in this system, as shown by profiles of the local density and orientational distribution functions. The phase diagram of the system, which includes the isotropic and nematic phases, is obtained in terms of the mean density and rigid-rod fraction of each molecule. The nematic-smectic transition is found to be second order. Since the smectic phase is induced solely by the difference in the rigidities, the onset of smectic ordering is shown to be an entropic effect and therefore does not have to rely on additional Flory-Huggins-type repulsive interactions between unlike chain segments. These findings are compared with other recent SCFT studies of similar copolymer models and with computer simulations of several molecular models.Comment: 13 pages, 8 figure

Self-Consistent Field study of Polyelectrolyte Brushes

We formulate a self-consistent field theory for polyelectrolyte brushes in the presence of counterions. We numerically solve the self-consistent field equations and study the monomer density profile, the distribution of counterions, and the total charge distribution. We study the scaling relations for the brush height and compare them to the prediction of other theories. We find a weak dependence of the brush height on the grafting density.We fit the counterion distribution outside the brush by the Gouy-Chapman solution for a virtual charged wall. We calculate the amount of counterions outside the brush and find that it saturates as the charge of the polyelectrolytes increases

Stabilization of tilt order by chain flexibility in Langmuir monolayers

Langmuir monolayers are modeled as systems of short chains, which are confined to a planar surface at one end, but free to move within the plane. The phase behavior is calculated in a mean field approximation, which combines the self consistent field method with elements of classical density functional theory. It is shown that phases with tilt order are unstable in systems of stiff chains, but can be stabilized by chain conformational entropy in systems of sufficiently flexible chains. The chain entropy is also responsible for the appearance of an additional untilted phase, the liquid expanded phase. The region of stability of the different phases is discussed, and their microscopic structure is analyzed in some detail.Comment: to appear in Phys. Rev.

Self-consistent field theory for the interactions between keratin intermediate filaments

Background: Keratins are important structural proteins found in skin, hair and nails. Keratin Intermediate Filaments are major components of corneocytes, nonviable horny cells of the Stratum Corneum, the outermost layer of skin. It is considered that interactions between unstructured domains of Keratin Intermediate Filaments are the key factor in maintaining the elasticity of the skin. Results: We have developed a model for the interactions between keratin intermediate filaments based on self-consistent field theory. The intermediate filaments are represented by charged surfaces, and the disordered terminal domains of the keratins are represented by charged heteropolymers grafted to these surfaces. We estimate the system is close to a charge compensation point where the heteropolymer grafting density is matched to the surface charge density. Using a protein model with amino acid resolution for the terminal domains, we find that the terminal chains can mediate a weak attraction between the keratin surfaces. The origin of the attraction is a combination of bridging and electrostatics. The attraction disappears when the system moves away from the charge compensation point, or when excess small ions and/or NMF-representing free amino acids are added. Conclusions: These results are in concordance with experimental observations, and support the idea that the interaction between keratin filaments, and ultimately in part the elastic properties of the keratin-containing tissue, is controlled by a combination of the physico-chemical properties of the disordered terminal domains and the composition of the medium in the inter-filament region. Keywords: Stratum corneum, Skin keratins, Intermediate filaments, Unstructured terminal domains, Bridging attractio