Crystallization-Driven Two-Dimensional Self-Assembly of Amphiphilic PCL‑b‑PEO Coated Gold Nanoparticles in Aqueous Solution

This Letter reports the first formation of free-standing plasmonic monolayer nanosheets by the self-assembly of AuNPs without assistance from a planar interface. The strategy involves the coating of poly­(caprolactone)-b-poly­(ethylene oxide) (PCL-b-PEO) diblock copolymers on AuNPs, followed by two-dimensional (2D) self-assembly of the resultant amphiphilic AuNPs in aqueous phase. The crystallization of the PCL blocks, affected by their grafting density and radius of gyration, drives the formation of the AuNP nanosheets, which undergoes a growth process of individual micelles to small nanosheets and eventually to large sheets. Due to the plasmonic coupling of AuNPs in close proximity, the AuNP nanosheets exhibit near-infrared (NIR) absorption with the maximum at about 700 nm. This study not only brings a new approach toward polymer–AuNP hybrid superstructures in solution, but also provides a new system for fundamental study on 2D self-assembly of AuNPs.