Enantioselective sensing and separation are major challenges. Nanochannel technologies are energy-saving and efficient for membrane separation. Herein, inspired by biological antiporter proteins, artificial nanochannels with antiporter behavior were fabricated for chiral sensing and separation. Tyrosine enantiomers were incorporated into hourglass-shaped nanochannels via stepwise modifications to fabricating multiligand-modified asymmetric channels. Chiral distinction of naproxen enantiomers was amplified in the l-Tyr/d-Tyr channels, with an enantioselectivity coefficient of 524, which was over 100-fold that of one-ligand-modified nanochannels. Furthermore, transport experiments evidenced the spontaneous antiport of naproxen enantiomers in the l-Tyr/d-Tyr channels. The racemic naproxen sample was separated via the chiral antiport process, with an enantiomeric excess of 71.2%. Further analysis using electro-osmotic flow experiments and finite-element simulations confirmed that the asymmetric modified multiligand was key to achieving separation of the naproxen enantiomers. We expect these multiligand-modified asymmetric nanochannels to provide insight into mimicking biological antiporter systems and offer an approach to energy-efficient and robust enantiomer separation.
Keywords: asymmetric modification; bionic antiporter; chiral separation; enantioselectivity; nanochannel.