Proton Transport from Dendritic Helical-Pore-Incorporated Polymersomes

The ability to add synthetic channels to polymersome (polymer vesicle) membranes could lead to novel membrane composites with unique selectivity and permeability. Proton transport through two different synthetic pores, self-assembled from either a dendritic dipeptide, (6Nf-3,4-3,5)12G2-CH2-Boc-L-Tyr-L-Ala-OMe, or a dendritic ester, (R)-4Bp-3,4-dm8G1-COOMe, incorporated into polymersome membranes are studied. Polymersomes; provide an excellent platform for studying such transport processes due to their robustness and mechanical and chemical stability compared to liposomes. It is found that the incorporated dendritic dipeptide and dendritic ester assemble into stable helical pores in the poly(ethylene oxide)-polybutadiene (PEO-PBD) polymersomes but not in the poly(2-methyloxazoline)-poly(dimethylsiloxane)-poly(2-methyl oxazoline) (PMOX-PDMS-PMOX) polymersomes. The incorporation is confirmed by circular dichroism (CD), changes in purely synthetic mechanical strength (e.g., areal expansion modulus) as assessed by micropipette aspiration, and cryo-TEM. In addition to the structural analyses, a transport measurement shows the incorporated dendritic helical pores allow facile transport of protons across the polymersome membranes after up to one month of storage. This integration of synthetic porous channels with polymersome substrates could provide a valuable tool for studying active transport processes in a composite membrane. These composites will ultimately expand the family of biologically inspired porous-membrane mimics.