Biomacromolecules, Vol.20, No.3, 1297-1307, 2019
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 (M-n,M-th approximate to 4900 g.mol(-1), D = 1.1) to prepare well-defined PDMS-b-pBEA diblock copolymers (D = 1.1) that were then substituted with 1-thio-beta-D-glucose or 1-thio-beta-D-galactose under facile conditions to yield PDMS-b-glycopolymers. Compositions possessing approximate to 25% of the glycopolymer block (by mass) were able to adopt a vesicular morphology in aqueous solution (approximate to 1210 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 demonstrated by turbidimetric experiments. Self-assembly of the same diblock copolymer compositions using an electroformation method yielded GGPs (ranging from 2-20 mu m in diameter). Interaction of these cell-sized polymersomes with fimH positive E. coli was then studied via confocal microscopy. The glucose-decorated GGPs were found to cluster upon addition of the bacteria, while galactose decorated GGPs could successfully interact with (and possibly immobilize) the bacteria without the onset of clustering. This demonstrates an opportunity to modulate the response of these synthetic cell mimics (protocells) toward biological entities through exploitation of selective ligand receptor interactions, which may be readily tuned through a considered choice of carbohydrate functionality.