We investigate the temperature dependency of the elastic constants of polyelectrolyte multilayers made from poly(diallyldimethylammonium chloride) (PDADMAC) and poly(styrenesulfonate) (PSS) by measuring the stiffness of individual hollow polyelectrolyte multilayer capsules in water using AFM force spectroscopy. Statistical analysis of the deformation data of the capsule ensemble combined with continuum mechanical modeling allows quantifying changes in the deformation characteristics and respective changes in the Young's modulus of the wall material. Our results show that the Young's modulus of the wall material decreases from the regime of 100 MPa to the order of MPa above 35 °C. This transition is reversible when returning to room temperature. The modulus becomes dependent on the deformation rate for high temperature, while it is not rate-dependent for low temperature. Therefore, we conclude that the wall material undergoes a melting process from a glassy to a viscoelastic fluid state. At the same time, a shrinking of the capsules is observed, which we explain qualitatively with surface tension effects. We discuss the implications of this finding in comparison with other multilayer systems and discuss novel strategies for shape control in PE multilayer systems based on these effects.

We present key factors that influence the mechanical stability of polyelectrolyte/nanoparticle composite microcontainers and their encapsulation behavior by thermal shrinkage. Poly(diallyldimethylammonium chloride) (PDADMAC), poly(styrenesulfonate) (PSS) microshells and citrate-stabilized gold nanoparticles are used. The presence of nanoparticles in the microshell renders the encapsulation process by heat-shrinking more difficult. The encapsulation efficiency is found to decrease as the concentration of material to be encapsulated increases. Increasing nanoparticle content in the microshell or the concentration of dextran increases the likelihood of getting fused and damaged capsules during encapsulation. On the other hand, mechanical studies show that doping microshells with gold nanoparticles significantly increases their stiffness and resistance to deformation. Internalization of capsules by cells supports that the incorporation of metal nanoparticles makes the shells more resistant to deformation. This work provides information of significant interest for the potential biomedical applications of polymeric microshells such as intracellular storage and delivery.

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In this paper, novel hollow polyelectrolyte multilayer tubes from poly(diallyldimethylammonium chloride) (PDADMAC), poly(styrene sulfonate) (PSS), and poly(allylamine hydrochloride) (PAH) were prepared: Readily available glass fiber templates are coated with polyelectrolytes using the layer-by-layer technique, followed by subsequent fiber dissolution. Depending on the composition of the polymeric multilayer, stable hollow tubes or tubes showing a pearling instability are observed. This instability corresponds to the Rayleigh instability and is a consequence of an increased mobility of the polyelectrolyte chains within the multilayer. The well-defined stable tubes were characterized with fluorescence microscopy, confocal laser scanning microscopy, and atomic force microscopy (AFM). The tubes were found to be remarkably free of defects, which results in an impermeable tube wall for even low molecular weight molecules. The mechanical properties of the tubes were determined with AFM force spectroscopy in water, and because continuum mechanical models apply, the Young's modulus of the wall material was determined. Additionally, scaling relations for the dependency of tube stiffness on diameter and wall thickness were validated. Because both parameters can be experimentally controlled by our approach, the deformability of the tubes can be varied over a broad range and adjusted for the particular needs.

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