Escape route: The laser‐initiated release of fluorescently labeled polymers from polyelectrolyte‐multilayer microcapsules is demonstrated inside living cancer cells. A polymer is incorporated in capsules with metal nanoparticles in their walls, which serve as light‐absorbing centers. The capsules are internalized by cells and near‐infrared light ruptures the walls of the capsules, thus releasing the content into the cells.

The temperature-dependent behavior of hollow polyelectrolyte multilayer capsules consisting of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(styrene sulfonate) (PSS) with a different number of layers was investigated in aqueous media using confocal laser scanning microscopy, scanning and transmission electron microscopy, atomic force microscopy, and elemental analysis. Capsules with an even number of layers exhibited a pronounced shrinking at elevated temperature resulting in a transition to a dense sphere, whereas capsules with an odd number of layers swelled during heating to 5-fold of their initial size followed by their rupture. This effect increases for odd layer numbers and decreases for even layer numbers with increasing layer number. According to elemental analysis, an excess of PDADMAC monomers exists within the multilayers of capsules with an odd number of layers leading to a repulsion between the positive charges, whereas shells with an even number of layers have a balanced ratio between the oppositely charged polyions, so that the temperature-dependent behavior is controlled by the different interactions between polyelectrolytes and the bulk water. At a certain temperature, the polyelectrolyte material softens thus facilitating any rearrangement. Besides incubation temperature, the duration of heating has an influence on the restructuring of the multilayers.

We present the concept of multifunctional nanoengineered polymer capsules and outline their applications as new drug delivery systems or supramolecular toolboxes containing, for example, enzymes capable of converting nontoxic prodrugs into toxic drugs at a designated location. Such functionalized nanocontainers offer a wide range of applications including enzymatic catalysis, controlled release, and directed drug delivery in medicine due to their multifunctionality. The unique advantage of capsules in comparison to other systems is that they can be functionalized or loaded simultaneously with the above-mentioned components, thus permitting multifunctional processes in single cells.

Polyelectrolyte multilayer capsules consisting of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(styrene sulfonate) (PSS) were used as a model system to study the temperature-dependent behavior of polyelectrolyte multilayer films in aqueous media. Shells terminated with PSS shrink upon heating, whereas PDADMAC-terminated ones swell, independent of the nature of the first layer, as measured by means of confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). Elemental analysis shows that the initial exponential layer growth of the film leads to a nearly neutral overall charge in the first case or a high positive excess charge in the latter. Depending on this overall charge either surface tension, due to an unfavorable polymer-solvent interaction, or electrostatics dominates, resulting in a shrinkage or expansion of capsules, respectively. Thus, it is possible to swell temperature-shrunk capsules by coating them with an additional PDADMAC layer. Micro-DSC measurements prove that polyelectrolyte multilayers undergo a glass transition in water at which the wall material softens, allowing the rearrangements to occur. It is found that the thermal history has an influence on the temperature behavior of capsules, especially on those ones terminated with PDADMAC. Also, the molecular weight of the polyelectrolytes affects the rearrangement of capsules. The lower the molecular weight and thus the smaller the entanglement of chains, the easier polyelectrolytes can rearrange.

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.

Fluchtweg: Die Laser‐initiierte Freisetzung von fluoreszenzmarkierten Polymeren aus Polyelektrolytmultischicht‐Mikrokapseln in lebenden Krebszellen wird vorgestellt. Ein Polymer wird in Kapseln eingeschlossen, die als Lichtabsorptionszentren fungierende Metallnanopartikel in den Wänden enthalten. Die Kapseln werden von Zellen aufgenommen, und Nah‐Infrarotlicht bricht die Kapselwände auf, sodass der Inhalt in die Zellen gelangt.

The temperature-dependent self-assembly of the single-chain bolaamphiphile dotriacontan-1,1'-diyl-bis[2-(trimethylammonio)ethyl phosphate] (PC-C32-PC) was investigated by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), X-ray scattering, rheological measurements, and dynamic light scattering (DLS). At room temperature this compound, in which two phosphocholine headgroups are connected by a C(32) alkyl chain, proved to be capable of gelling water very efficiently by forming a dense network of nanofibers (Kohler et al. Angew. Chem., Int. Ed. 2004, 43, 245). A specific feature of this self-assembly process is that it is not driven by hydrogen bonds but solely by hydrophobic interactions of the long alkyl chains. The nanofibers have a thickness of roughly the molecular length and show a helical superstructure. A model for the molecular structure of the fibrils which considers the extreme constitution of the bolaamphiphile is proposed. Upon heating the suspensions three different phase transitions can be detected. Above 49 degrees C, the temperature of the main transition where the alkyl chains become "fluid", a clear low-viscosity solution is obtained due to a breakdown of the fibrils into smaller aggregates. Through mechanical stress the gel structure can be destroyed as well, indicating a low stability of these fibers. The gel formation is reversible, but as a drastic rearrangement of the molecules takes place, metastable states occur.

A matter of taste: The sweetner saccharin (a cyclic sulfimide, see picture) is nearly completely absorbed and eliminated through the urine, and is thus exposed to many different proteins in the body. It binds at nanomolar levels to some carbonic anhydrases and this provokes the question of its inert properties. It is known that the plasma level slowly decreases after oral dosing, and CAVI binding could explain its unpleasant metallic aftertaste.