Synthesis, nanoprecipitation and pH sensitivity of amphiphilic linear-dendritic hybrid polymers and hyperbranched-polydendrons containing tertiary amine functional dendronsElectronic supplementary information (ESI) available: Materials, experimental procedures and characterization data with assignments. See DOI: 10.1039/c5sm00673b

The combination of linear polymers with dendritic chain-ends has led to numerous studies of linear-dendritic polymer hybrid materials. Interchain branching within the linear segment of these materials has recently extended this concept to the formation of soluble hyperbranched-polydendrons. Here, the introduction of amphiphilicity into hyperbranched-polydendrons has been achieved for the first time through the use of tertiary amine functional dendritic chain-ends and branched hydrophobic polymer segments. The synthesis and aqueous nanoprecipitation of these branched materials is compared with their linear-dendritic polymer analogues, showing that chain-end chemistry/generation, precipitation medium pH and polymer architecture are all capable of influencing the ability to generate nanoparticles, the resulting nanoparticle diameter and dispersity, and subsequent response to changes in pH. Tertiary amine functional hyperbranched-polydendrons with pH-responsive chain ends and hydrophobic cores have been synthesised. The branched architecture leads to enhanced self-assembly over linear-dendritic analogues.