Aggregative Growth of Oligopeptide‐Protected Gold Nanoclusters into Plasmonic Particles

Abstract

The stimuli response of nanomaterials represents a highly appealing characteristic, whereas the practical applications (in catalysis, biosensing etc.) are largely restricted by the limited understanding on the recognition mechanism. Herein, we report a pH‐regulated size evolution from atomically precise Au nanoclusters (NCs) to plasmonic nanoparticles (NPs). The spectral monitoring demonstrates a three‐stage aggregative growth pathway. First, the non‐covalent interactions among the exterior oligopeptide ligands are gradually enhanced with the increased alkalinity, and then the Au−S bonding is partially disrupted, with the exposed Au atoms aggregating to form relatively larger, polydisperse clusters under weak alkaline conditions. Finally, size‐redistribution occurs slowly under strong alkaline conditions to form the plasmonic particles. The controllable transition sheds light on the transition characteristics from molecular state to metallic state of Au nanomaterials.

Protein-Directed Au(0)-Rich Gold Nanoclusters as Ratiometric Luminescence Sensors for Auric Ions via Comproportionation-Induced Emission Enhancement

“…35 Thus, it is likely that the modification of Au(I) content via surface engineering would have a significant effect on the photo-physical properties of Au NCs@BSA. Furthermore, the role of solution alkalinity goes beyond the activation of protein reduction capabilities and the exposure of Au binding sites, 36 as it also increases the available space for Au NC formation. 37 Control of reacting pH should, therefore, represent an ideal tool for surface Au(I) engineering.…”