Effect of environmental parameters on the nano mechanical properties of hyaluronic acid/poly(l-lysine) multilayers.

Atomic force microscopy (AFM) was used to determine the mechanical properties as the indentation modulus of native and crosslinked poly(l-lysine) (PLL)/hyaluronic acid (HA) multilayer films by static force measurements. The influence of the surrounding medium on the mechanical properties of the films after preparation is investigated. The indentation modulus of native and crosslinked film was measured at different pH values, ionic strengths and temperatures. The native HA/PLL films, which behave like a physical gel, show the highest values of the indentation modulus for an intermediate pH value and low ionic strength. Any changes in the pH or an increase in the ionic strength/temperature decreases the measured indentation modulus. In contrast, the crosslinked films show an increase by a factor of 80 in the indentation modulus but no response to changes in the pH, ionic strength or temperature; they behave like a chemical gel. The pH, ionic strength and temperature used in this work are close to the in vivo conditions and thus give a fundamental point of view on the nanomechanical response of the PLL/HA films. Furthermore, information about the mechanical properties can be used for the understanding and manipulation of cell adhesion.

Adhesion property profiles of supported thin polymer films.

Polymer coatings are frequently utilized to control and modify substrate properties. The performance of the coatings is often determined by the first polymer layers between the substrate and the bulk polymer material, which are termed interphase. Standard methods have failed to completely characterize this interphase, because its properties change significantly over a few nanometers. Here we determine the spatially resolved adhesion properties of the interphase in polyelectrolyte multilayers (PEMs) by desorbing a single polymer covalently bound to an atomic force microscope cantilever tip from PEMs with varying thickness. We show that the adhesion properties of the first few layers (up to three double layers) is dominated by the surface potential of the substrate, while thicker PEMs are controlled by cohesion in between the PEM polymers. For cohesion, the local film conformation is the crucial parameter. This finding is generalized by utilizing oligoelectrolyte multilayer (OEM) as coatings and both hydrophilic and hydrophobic polymers as polymeric force sensors.

Interaction forces between silica surfaces in cationic surfactant solutions: an atomic force microscopy study.

The interaction forces between silicon oxide surfaces in the presence of surfactant solutions were studied. Based on the qualitative and quantitative analysis of these interaction forces the correlation with the structure of the aggregates on the surfaces is analyzed. A colloidal probe atomic force microscope (AFM) was used to measure the forces between two colloidal silica particles and between a colloidal particle and a silicon wafer in the presence of hexadecyltrimethylammonium bromide (CTAB) at concentrations between 0.005 mM and 1.2 mM. Different interaction forces were obtained for the silica particle-silica particle system when compared to those for the silica particle-silicon wafer system for the same studied concentration. This indicates that the silica particles and the silicon wafer have different aggregate morphologies on their surfaces. The point of zero charge (pzc) was obtained at 0.05 mM CTAB concentration for the silica particles and at 0.3mM for the silica particle-silicon wafer system. This indicates a higher charge at the silicon wafer than at the silica particles. The observed long range attractions are explained by nanobubbles present at the silicon oxide surfaces and/or by attractive electrostatic interactions between the surfaces, induced by oppositely charged patches at the opposing Si oxide surfaces.

Impact of surface charges on the solvation forces in confined colloidal solutions.

Combining computer simulations and experiments we address the impact of charged surfaces on the solvation forces of a confined, charged colloidal suspension (slit-pore geometry). Investigations based on the colloidal-probe atomic-force-microscope technique indicate that an increase in surface charges markedly enhances the oscillations of the force in terms of their amplitude. To understand this effect on a theoretical level we perform grand-canonical Monte-Carlo simulations (GCMC) of a coarse-grained model system. It turns out that various established approaches of the interaction between a charged colloid and a charged wall, such as linearized Poisson-Boltzmann (PB) theory involving the bulk screening length, do not reproduce the experimental observations. We thus introduce a modified PB potential with a space-dependent screening parameter. The latter takes into account, in an approximate way, the fact that the charged walls release additional (wall) counterions which accumulate in a thin layer at the surface(s). The resulting, still purely repulsive fluid-wall potential displays a nonmonotonic behavior as function of the surface potential with respect to the strength and range of repulsion. GCMC simulations based on this potential reproduce the experimentally observed charge-induced enhancement in the force oscillations. We also show, both by experiment and by simulations, that the asymptotic wave- and decay length of the oscillating force do not change with the wall charge, in agreement with predictions from density functional theory.

Internal structure of polyelectrolyte multilayer assemblies.

The paper deals with the correlation between the internal structure and dynamics of polyelectrolyte multilayers on one hand and their functional properties on the other hand. It considers different concepts of multilayer formation like driving forces, adsorption kinetics, mode of growth and stability aspects. A further focus is the control of internal structure and dynamics which is of high impact with respect to the design of stimuli-responsive material.

Effect of interface modification on forces in foam films and wetting films.

The paper reviews the effect of the surface composition on forces within aqueous foam and wetting films. In both types of films the charge of the air/water interface is varied by different surfactants. In wetting films the charge and the hydrophobicity of the solid substrate is changed by polymer coatings. The addition of polymers to foam films leads to the formation of surface active polymer/surfactant complexes or to depletion near the interfaces. The dissolution of polyelectrolytes within the film bulk can lead to structural forces. The selection of studies is made with respect to two questions: (1) What is the reason for charges at the air/water interface and (2) what is the mechanism of long-range hydrophobic interaction?