In article number 1900187 by Clive J. Roberts, Ricky D. Wildman and co‐workers report an entirely new approach to formulating and controlling drug release from 3D printed systems/implants. This approach allows for hierarchical control over release, by exercising control over composition of a printed system over multiple length scales through molecular to macroscopic.

The ability of poly(triazolyl methacrylate) glycopolymers to function as unimolecular targeted carriers for hydrophobic guest molecules was investigated using a combination of experimental and computational techniques.

A small library of thermoresponsive amphiphilic copolymers based on polylactide-block-poly((2-(2-methoxyethoxy)ethyl methacrylate)-co-(oligoethylene glycol methacrylate)) (PLA-b-P(DEGMA)-co-(OEGMA)), was synthesised by copper-mediated controlled radical polymerisation (CRP) with increasing ratios of OEGMA : DEGMA. These polymers were combined in two ways to form nanoparticles with controllable thermal transition temperatures as measured by particle aggregation. The first technique involved the blending of two (PLA-b-P(DEGMA)-co-(OEGMA)) polymers together prior to assembling nanoparticles (NPs). The second method involved mixing pre-formed nanoparticles of single (PLA-b-P(DEGMA)-co-(OEGMA)) polymers. The observed critical aggregation temperature T did not change in a linear relationship with the ratios of each copolymer either in the nanoparticles blended from different copolymers or in the mixtures of pre-formed nanoparticles. However, where co-polymer mixtures were based on (OEG)MA ratios within 5-10 mole%, a linear relationship between (OEG)MA composition in the blends and T was obtained. The data suggest that OEGMA-based copolymers are tunable over a wide temperature range given suitable co-monomer content in the linear polymers or nanoparticles. Moreover, the thermal transitions of the nanoparticles were reversible and repeatable, with the cloud point curves being essentially invariant across at least three heating and cooling cycles, and a selected nanoparticle formulation was found to be readily endocytosed in representative cancer cells and fibroblasts.

Three different routes are presented for the synthesis of functional RAFT agents from N-substituted maleimides, which are then used to synthesise α,β,ω-functional RAFT polymers.

No abstract