Dopamine-Mediated Assembly of Citrate-Capped Plasmonic Nanoparticles into Stable Core–Shell Nanoworms for Intracellular Applications

Plasmonic nanochains, derived from the one-dimensional assembly of individual plasmonic nanoparticles (NPs), remain infrequently explored in biological investigations due to their limited colloidal stability, ineffective cellular uptake, and susceptibility to intracellular disassembly. We report the synthesis of polydopamine (PDA)-coated plasmonic "nanoworms" (NWs) by sonicating citrate-capped gold (Cit-Au) NPs in a concentrated dopamine (DA) solution under alkaline conditions. DA mediates the assembly of Cit-Au NPs into Au NWs within 1 min, and subsequent self-polymerization of DA for 60 min enables the growth of an outer conformal PDA shell that imparts stability to the inner Au NW structure in solution, yielding "core-shell" Au@PDA NWs with predominantly 4-5 Au cores per worm. Our method supports the preparation of monometallic Au@PDA NWs with different core sizes and bimetallic PDA-coated NWs with Au and silver cores. The protonated primary amine and catechol groups of DA, with their ability to interact with Cit anions via hydrogen bonding and electrostatic attraction, are critical to assembly. When compared to unassembled PDA-coated Au NPs, our Au@PDA NWs scatter visible light and absorb near-infrared light more intensely and enter HeLa cancer cells more abundantly. Au@PDA NWs cross the cell membrane as intact entities primarily via macropinocytosis, mostly retain their inner NW structure and outer PDA shell inside the cell for 24 h, and do not induce noticeable cytotoxicity. We showcase three intracellular applications of Au@PDA NWs, including label-free dark-field scattering cell imaging, delivery of water-insoluble cargos without pronounced localization in acidic compartments, and photothermal killing of cancer cells.