DNA-Condensed Plasmonic Supraballs Transparent to Molecules

DNA nanotechnology offers an unrivaled programmability of plasmonic nanoassemblies based on encodable Watson-Crick basepairing. However, it is very challenging to build rigidified three-dimensional supracolloidal assemblies with strong electromagnetic coupling and a self-confined exterior shape. We herein report an alternative strategy based on a DNA condensation reaction to make such structures. Using DNA-grafted gold nanoparticles as building blocks and metal ions with suitable phosphate affinities as abiological DNA-bonding agents, a seedless growth of spheroidal supraparticles is realized via metal-ion-induced DNA condensation. Some governing rules are disclosed in this process, including kinetic and thermodynamic effects stemming from electrostatic and coordinative forces with different interaction ranges. The supraballs are tailorable by adjusting the volumetric ratio between DNA grafts and gold cores and by overgrowing extra gold layers toward tunable plasmon coupling. Various appealing and highly desirable properties are achieved for the resulting metaballs, including (i) chemical reversibility and fixation ability, (ii) stability against denaturant, salt, and molecular adsorbates, (iii) enriched and continuously tunable plasmonic hotspots, (iv) permeability to small guest molecules and antifoulingness against protein contaminates, and (v) Raman-enhancing and photocatalytic activities. Innovative applications are thus foreseeable for this emerging class of meta-assemblies in contrast to what is achieved by DNA-basepaired ones.