Synthesis and Characterization of Shell-Cross-Linked Glycopolymer Bilayer Vesicles

Vesicles composed of self-assembled lipids or amphiphilic polymers have significant potential in applications such as delivery of cargo for therapeutics. However, they are fragile under physiological conditions such as inside living cells or the bloodstream, in which a vast number of other molecules are present in high concentrations. This is because vesicles are in dynamic equilibrium between unimers and vesicles. Therefore, the development of more robust vesicles by covalent cross-linking of the shell was focused on. Cross-linked polymer vesicles were prepared by the self-assembly of maltopentaose-b-poly(propylene glycol) followed by the reaction between divinyl sulfone and the hydroxyl group in a maltopentaose unit. It was found that two equivalents of DVS to the polymer is an optimal condition for the cross-linking without changing in size. The bilayer structures were retained after the cross-linking reactions. Importantly, the cross-linked polymer vesicles retained their size and polydispersity even in 50:50 v/v methanol/water solution. This work highlights the potential of the divinyl sulfone shell cross-link as a promising tool for stabilization of glycopolymer vesicles.