Highly Enantioselective Graphene-Based Chemical Sensors Prepared by Chiral Noncovalent Functionalization

Abstract

As a basic characteristic of the natural environment and living matter, chirality has been used in various scientific and technological fields. Chiral discrimination is of particular interest owing to its importance in catalysis, organic synthesis, biomedicine, and pharmaceutics. However, it is still very challenging to effectively and selectively sense and separate different enantiomers. Here, enantio-differentiating chemosensor systems have been developed through spontaneous chiral functionalization of the surface of graphene field-effect transistors (GFETs). GFET sensors functionalized using noncovalent interactions between graphene and a newly synthesized chiral-functionalized pyrene material, Boc-L-Phe-Pyrene, exhibit highly enantioselective detection of natural acryclic monoterpenoid enantiomers, that is, (R)-(+)- and (S)-(-)-beta-citronellol. On the basis of a computational study, the origin of enantio-differentiation is assigned to the discriminable charge transfer from (R)-(+)- or (S)-(-)-beta-citronellol into graphene with a significant difference in binding strength depending on surface morphology. The chemosensor system developed herein has great potential to be applied in miniaturized and rapid enantioselective sensing with high sensitivity and selectivity.