Surface Topographical Engineering of Chiral Au Nanocrystals with Chiral Hot Spots for Plasmon-Enhanced Chiral Discrimination.

Surface roughness in chiral plasmonic nanostructures generates asymmetrical localized electromagnetic fields, which hold great promise for applications in chiral recognition, chiroptical spectroscopic sensing, and enantioselective photocatalysis. In this study, we develop a surface topographical engineering approach to precisely manipulate the surface structures of chiral Au nanocrystals. Through carefully controlling the amounts of l- or d-cystine (Cys) and the seed solution in the growth process, we successfully synthesize chiral Au nanocrystals with highly disordered, ordered, and less ordered wrinkled surfaces. An underlying principle governing the relationship between surface roughness, orderliness, and chiroptical response is also proposed. More importantly, the chiral ordered wrinkles on the surfaces of the nanocrystals generate asymmetrical localized electronic fields with enhanced intensity, which achieve excellent plasmon-enhanced chiral discrimination ability for penicillamine (Pen) enantiomers. This work offers exciting prospects for manipulating the surface structures of chiral nanocrystals and designing highly sensitive plasmon-enhanced enantioselective sensors with chiral hot spots.