Polydimethylsiloxane-Based Giant Glycosylated Polymersomes with Tunable Bacterial Affinity

A synthetic cell mimic in the form of giant glycosylated polymersomes (GGPs) comprised of a novel amphiphilic diblock copolymer is reported. A synthetic approach involving a poly(dimethylsiloxane) (PDMS) macro-chain transfer agent (macroCTA) and postpolymerization modification was used to marry the hydrophobic and highly flexible properties of PDMS with the biological activity of glycopolymers. 2-Bromoethyl acrylate (BEA) was first polymerized using a PDMS macroCTA (Mn,th ≈ 4900 g·mol–1, Đ = 1.1) to prepare well-defined PDMS-b-pBEA diblock copolymers (Đ = 1.1) that were then substituted with 1-thio-β-d-glucose or 1-thio-β-d-galactose under facile conditions to yield PDMS-b-glycopolymers. Compositions possessing ≈25% of the glycopolymer block (by mass) were able to adopt a vesicular morphology in aqueous solution (≈210 nm in diameter), as indicated by TEM and light scattering techniques. The resulting carbohydrate-decorated polymersomes exhibited selective binding with the lectin concanavalin A (Con A), as...