Hyperbranched polydendrons: a new controlled macromolecular architecture with self-assembly in water and organic solvents

A new macromolecular architecture (hyperbranched polydendrons) is presented. Combining aspects of linear-dendritic hybrids, controlled radical polymerisation and branched vinyl polymerisation, the materials have very high molecular weight (Mw > 1 MDa) and surface functionality. Although dispersities are broad (Đ up to 25) the structures behave with remarkable uniformity upon manipulation of solvent environment. Comparisons of conventional linear-dendritic hybrids and hyperbranched polydendrons are presented, including aspects of their synthesis. Under solvent exchange in organic media, a reversible self-assembly to form monodispersed nanoparticles (PDI as low as 0.013) is observed. Self-assembly and encapsulation is also observed during aqueous nanoprecipitation of the hyperbranched materials, with nanoparticle size (diameters from 60–140 nm) controlled through modification of precipitation conditions and the generation of the ideally branched dendrons at one end of each primary chain. The aqueous nanoparticles are highly stable and offer considerable opportunities for tailored functionality and future advanced applications.