Controllable “Clicked-to-Assembled” Plasmonic Core–Satellite Nanostructures and Its Surface-Enhanced Fluorescence in Living Cells

[Image: see text] The assembly of noble-metal core–satellite (CS) nanostructures is an appealing means to control their plasmonic properties for their applications such as surface-enhanced fluorescence or Raman scattering. However, till now there is a lack of some rapid or convenient methods to construct stable CS nanostructures. Here, we proposed a “clicked-to-assembly” strategy based on the fast and specific “click chemistry” reaction between trans-cyclooctene (TCO) and 1,2,4,5-tetrazine (Tz). The CS nanostructures were constructed within 8 min by simple mixing of TCO- or Tz-modified nanoparticles (TCO-NPs or Tz-NPs) without any catalysts or heating required. Transmission electron microscopy experiments show that the constructed CS nanostructures are uniform, and particularly the number of “satellite” nanoparticles in the core surface is controllable by simply adjusting the feeding ratio of TCO-NPs or Tz-NPs in the reaction. The strong surface plasmon coupling effect (SPCE) was observed in these CS nanostructures, which was dependent on the coverage degree, size and composition of the satellite, and core NPs. The nanostructures with tuned surface plasmon resonance (SPR) effect were tried for the surface-enhanced fluorescence in living cells. Such well-defined CS nanostructures could potentially serve as efficient SPR-enhanced fluorescent probes as diagnostics or biomedical imaging agents in nanomedicine.