Xanthate functional dendritic ATRP macroinitiators, synthesised via a new orthogonal strategy, have been used to form a library of linear-dendritic hybrids via one-pot, post polymerisation, deprotection/acrylate Michael addition.

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.

Introducing multiple reactive functional groups at the periphery of dendrimer materials presents considerable challenges if the functionality is able to self-react. An efficient and facile approach to introducing masked thiols at the surface of polyester dendrimers is presented. One-pot, deprotection/thiol-acrylate Michael addition from the xanthate-functional dendritic substrates (generation zero to two) has been achieved for the first time, with high efficiency demonstrated using three acrylates of varying chemistry and avoiding disulfide formation.

Accurate analysis of model systems by MALDI-TOF has established the diversity of structures formed during post-synthesis functionalisation of complex polymer architectures. NMR studies alone are shown to be highly misleading.