Influence of Host–Guest Interaction between Chiral Selectors and Probes on the Enantioseparation Properties of Graphene Oxide Membranes

Graphene oxide (GO)-based membranes have displayed superior performances in the chiral resolution compared with conventional polymer-based and inorganic membranes. However, the effect of the host–guest interaction between chiral selectors and probes on the enantioseparation properties of GO-based membranes remains to be established. In this work, l-phenylalanine (l-Phe, as the chiral selector)-modified GO-based (l-Phe-GO) membranes were fabricated, and their enantioseparation performances toward various enantiomers, that is, d- and l-phenylalanine (d- and l-Phe), d- and l-methionine (d- and l-Met), N-acyl-d-phenylalanine (N-acyl-d-Phe) and N-acyl-l-phenylalanine (N-acyl-l-Phe), and N-acyl-d-methionine (N-acyl-d-Met) and N-acyl-l-methionine (N-acyl-l-Met), were detected. Results show that (i) l-Phe is preferential to transport d-enantiomers relative to l-enantiomers; (ii) as far as d-enantiomers are concerned, the d-Phe-like enantiomers move faster than d-Met-like ones through the l-Phe-GO membrane owing to their different host–guest interactions. The strength of interactions between chiral selectors and probes was further confirmed from both experimental and theoretical standpoints. In the former case, the enantioselective adsorption of l-Phe-GO nanosheets toward the aforementioned enantiomers demonstrates that l-Phe delivers a higher adsorption capacity to d-enantiomers relative to l-enantiomers, and meanwhile, d-Phe-like enantiomers are better than d-Met-like enantiomers in the adsorption capacity. In the latter case, the chiral separation mechanism is clarified using the periodical density functional theory (DFT) calculation, indicating that l-Phe interacts with d-enantiomers more strongly than l-enantiomers. Especially, our calculations unveil that the difference in the interaction strength is principally dominated by the nonstereoselective interactions between chiral probes and the GO surface. Therefore, our findings suggest that the nonstereoselective weak interaction can be employed to improve the enantioselectivity of GO-based membranes.