Controlled biomolecules separation by CO₂-responsive block copolymer membranes

The intelligent responsive membranes have aroused much attention due to their distinctive capability to reversibly change separation performances under the stimulation of ambient environment. Especially, the responsive membranes derived from block copolymers, which have regular nanoporous structures, display great potential in high-precision controllable separation. Herein, we use CO₂ gas as the non-toxic, mild stimulus, and develop the responsive membranes from a block copolymer of poly(2-diethylaminoethyl methacrylate)-block-polystyrene (PDEAEMA-b-PS) by the selective swelling method. The membranes exhibit a bi-continuous nanoporous structure and the surfaces and pore walls are rich with CO₂-responsive PDEAEMA chains. Based on the reversible conformation transition of PDEAEMA chains between the collapsed state and extended state upon CO₂/N₂ stimulation, the membranes achieve the controllable regulation on the water permeances from ∼100 to ∼2100 L⋅h⁻¹⋅m⁻²⋅bar⁻¹, also realize the blocking/passing switch for varied proteins. More importantly, the extended PDEAEMA chains shrink the effective pore size down to less than 5 nm, moving the separation scope from ultrafiltration to tight-ultrafiltration. Thus, the membranes are capable to separate macromolecular proteins with small molecule polypeptide and vitamin with high separation efficiencies, demonstrating their application prospect in precise separation and fractionation of biomolecules.