Synthesis of Functional Miktoarm Star Polymers in an Automated Parallel Synthesizer

A feasibility study for the synthesis of well-defined miktoarm star polymers containing peptide arms in an automated parallel synthesizer is reported. A series of linear homo- and block (co-)polymers were prepared in the presence of commercial or peptide-functionalized reversible addition-fragmentation chain transfer (RAFT) agents. Thereafter, miktoarm star polymers were obtained by cross-linking different combinations of the abovementioned linear polymers using N, N'-bis(acryloyl) cystamine (BAC) as a redox responsive cross-linker. The described automated synthesis can be regarded as a proof-of-principle technique that next to emerging automated polymer purification and machine learning approaches could be useful to potentiate the development of autonomous methods for accessing systematic and comprehensive (peptide-)functionalized star polymer libraries. With these approaches hundreds of candidates of these complex polymer architectures could be rapidly synthesized, screened and optimized for different applications.