Precise Construction of Chiral Plasmonic Nanoparticles for Enantioselective Discrimination.

Chiral plasmonic nanostructures exhibit potential in the advanced manufacturing industry, due to their fascinating characteristics. However, the limitation of existing fabrication methods as difficulty to precisely manipulate chiral nanostructures at the nanoscale restricts their application and optimization of performance. In this work, we report a simple and robust route for the precise construction of chiral Au nanoparticles (NPs), employing star-like block copolymers with well-defined structures as chiral templates. The globular unimolecular micelles as nanoreactors enabled control over the size, shape, and chirality of in situ grown nanocrystals. Utilizing the chiral anisotropy property of surface-enhanced Raman scattering (SERS), the enantioselective discrimination on various substrates was accomplished with an enhancement factor over 9.3 × 106. NPs with a smaller size exhibited strengthened Raman enhancement and chiral recognition. Furthermore, these chiral unimolecular-micelle-based templates with high efficiency and strong controllability could pave the way for tailor-made chiral nanomaterials.

Chiral Confined Unimolecular Micelles for Controlled In Situ Fabrication of Optically Active Hybrid Nanostructures.

Functional nanomaterials made by chiral induction have attracted extensive attention because of their intriguing characteristics and potential applications. However, the precise and controllable fabrication of chiral nanomaterials still remains challenging but is highly desired. In this study, chiral unimolecular micelles with different molecular weights and chiroptical activities were prepared by photoinduced atom transfer radical polymerization (photoATRP). Through nanoconfined growth, the chiral plasmonic nanoparticle assemblies with predesigned size and morphology were prepared using chiral unimolecular micelles as nanoreactors. The controllability over chiral assemblies and the size effect on chiroptical properties were also investigated. Furthermore, chiral complexes with absorption asymmetry and circularly polarized luminescence (glum = 4.25 × 10-4) were easily constructed via mixing of organic fluorescent molecules and chiral templates based on intermolecular hydrogen bonds. Such results indicated that our unimolecular-micelle-based templates enable the controllable preparation of both inorganic and organic chiral nanostructures with tailored dimensions, sizes, compositions, and optical activities.