Hierarchical polyion complex vesicles from PAMAM dendrimers.

Hierarchical dendrimer-based polyion complex (PIC) vesicles with multiple compartments have attracted considerable attention as functional delivery vehicles and nano-carriers. Formation of these vesicles relies on the electrostatic assembly of asymmetric polyelectrolytes, namely branched dendrimers with linear polyion-neutral diblock copolymers. However, successful incorporation of dendrimers in vesicle lamellae is challenging due to the compact structure of dendrimers, and therefore, vesicles reported so far are prepared mainly with low generation dendrimers which lack the cavity required for carrier functions. Here, we present a new assembly combination of amine-terminated dendrimer polyamidoamine (PAMAM) with polyion-neutral diblock copolymer poly (styrene sulphonate-b-ethylene oxide) (PSS-b-PEO). The strong charge interaction between the building blocks leads to stable and well-defined PIC vesicles that can tolerate not only different PSS block lengths but, more importantly, also different dendrimer generations from 2 to 7. As a consequence, high generation dendrimers with a cavity can be packed in the vesicle wall, and one obtains hierarchical PIC vesicles with multiple compartments, namely the dendrimer cavity for loading small hydrophobic cargo, and the vesicle lumen for encapsulating hydrophilic macromolecules. Our study demonstrates that combining proper building blocks enables to manipulate the charge interactions, which is essential for controlling the dendrimer packing and the formation of PIC vesicles. These findings should be helpful for understanding the assembly of asymmetric (linear / branched) polyelectrolyte complexes, as well as for designing new hierarchical PIC vesicles for controlled delivery of multiple active substances.