Frédéric Dubreuil

Elastic properties of polyelectrolyte capsules studied by atomic-force microscopy and RICM

Abstract.Mechanical properties of polyelectrolyte multilayer capsules were studied using a new method combining atomic-force microscopy and reflection interference contrast microscopy. By measuring the force vs. deformation for poly(styrene sulfonate)/poly(allylamine) capsules the existence of different deformation regimes depending on the applied deformation was shown. The present paper focuses on the small-deformation regime. The elastic response of the deformed capsule was studied as a function of the wall thickness and the capsule size, and showed the theoretically expected variations. The Young modulus obtained from the experiments ranges between 1.3 and 1.9 GPa.

Mechanics of artificial microcapsules

In recent years, an increasing number of microcapsule systems have been realized and have found applications in various fields of research and technology. Amongst others, polyelectrolyte multilayer capsules (PMCs) offer a great variety of materials and superior control over the wall thicknesses. We present here a review on the different techniques that are available for characterizing the mechanical properties of PMCs. We compare results that were obtained using these techniques on the same system, namely PMCs made from polyallylamine and polystyrenesulfonate multilayers and discuss perspectives of the field.

Designing Hyaluronic Acid-Based Layer-by-Layer Capsules as a Carrier for Intracellular Drug Delivery

Polyelectrolyte microcapsules were prepared by the layer-by-layer assembly of hyaluronic acid (HA) and a polycationic polymer, poly(allylamine) (PAH) or poly(lysine) (PLL). The influence of the polycationic partner on the morphology, stability, permeability properties, and enzymatic degradation of microcapsules was thoroughly analyzed. It was found that these properties could be tuned by shell cross-linking. Confocal microscopy studies of cellular uptake of the capsules showed that the polyelectrolyte shells remain stable outside the cells but readily break open once internalized by cells, suggesting their potential as carrier for intracellular drug delivery.

Mechanical Properties of Freestanding Polyelectrolyte Capsules: a Quantitative Approach Based on Shell Theory

In this paper we report on AFM force spectroscopy measurements on hollow polymeric spheres of colloidal dimensions made from polyelectrolyte multilayers of polyallylamine and polystyrenesulfonate in water. We find that the shells show a linear force-deformation characteristic for deformations of the order of the shell wall thickness. This experimental outcome is discussed in terms of analytical results of continuum mechanics, in particular the scaling behaviour of the shell spring constant with wall thickness, shell radius and speed of the deformation is analysed. The experimental results agree well with the predictions of Reissner for thin shells and allow us to rescale our stiffness data such that a master curve of shell stiffness is obtained. The result of Reissner is strictly valid only for point like loading situations, while in our experiments a more extended plate like load is applied. Experimentally we find indeed little influence of the probe geometry on the shell spring constant. This result agrees well with finite element (FE) calculations that show that the Reissner result is a good approximation also for non point like loading situations, as long as small deformations are considered.

Probing multivalent host-guest interactions between modified polymer layers by direct force measurement.

The adhesion behavior between modified polysaccharide layers capable of forming host-guest complexes has been determined by direct force measurements with the atomic force microscope (AFM). Polysaccharides bearing either host or guest moieties were obtained by derivatization of chitosan with pendant β-cyclodextrin (CD) and adamantane (AD) moieties, respectively. These modified polysaccharides were covalently immobilized either to flat surfaces or to AFM-probes. The number of interacting polymer segments has been reduced significantly by covalently immobilizing chitosan to an AFM-tip with small radius and measuring the forces between the protruding polymer segments and a chitosan layer immobilized to a flat surface. By this approach, it was possible to determine the interaction between polymer layers on the level of single polymer strands. To separate contributions to the adhesion due to the formation of host-guest complexes from unspecific interactions, we performed measurements between various combinations of chitosan derivatives. With the same polymer probe of adamantane-modified chitosan, the interaction against a number of different chitosan layers has been determined, including ones that are not able to form host-guest complexes, such as unmodified chitosan or β-cyclodextrin modified chitosan, which has been blocked previously by addition of adamantane. The resulting adhesion behavior has been analyzed in terms of the total work of adhesion, the number of rupture events, and the corresponding lengths of the polymer segments as well as rupture forces. A clear difference has been found for systems where the formation of host-guest complexes is possible in comparison to the absence of specific multivalent interaction between the polysaccharide layers. In particular, the work of adhesion is increasing up to an order of magnitude upon the formation of host-guest complexes between the chitosan layers.