Hydrophobic Gold Nanoparticles with Intrinsic Chirality for the Efficient Fabrication of Chiral Plasmonic Nanocomposites

ACS Appl Mater Interfaces. 2022 Oct 28;14(44):50013-50023. doi: 10.1021/acsami.2c11925. Online ahead of print.

Abstract

The development of plasmonic nanomaterials with chiral geometry has drawn extensive attention owing to their practical implications in chiral catalysis, chiral metamaterials, or enantioselective biosensing and medicine. However, due to the lack of effective synthesis methods of hydrophobic nanoparticles (NPs) showing intrinsic, plasmonic chirality, their applications are currently limited to aqueous systems. In this work, we resolve the problem of achieving hydrophobic Au NPs with intrinsic chirality by efficient phase transfer of water-soluble NPs using low molecular weight, liquid crystal-like ligands. We confirmed that, after the phase transfer, Au NPs preserve strong, far-field circular dichroism (CD) signals, attesting their chiral geometry. The universality of the method is exemplified by using different types of NPs and ligands. We further highlight the potential of the proposed approach to realize chiral plasmonic, inorganic/organic nanocomposites with block copolymers, liquid crystals, and compounds forming physical gels. All soft matter composites sustain plasmonic CD signals with electron microscopies confirming well-dispersed nanoinclusions. The developed methodology allows us to expand the portfolio of plasmonic NPs with intrinsic structural chirality, thereby broadening the scope of their applications toward soft-matter based systems.

Keywords: block copolymers; chiral metamolecules; chirality transfer; circular dichroism; gels; liquid crystals; phase transfer; reconfigurable nanostructures; supramolecular chirality.