LAUSR

Nanoparticle superlattice assembly has been proposed as an ideal means of programming material properties as a function of hierarchical organization of different building blocks. While many investigations have focused on electromagnetic, optical, and transport behaviors, nanoscale self-assembly via supramolecular interactions is also a potentially desirable method to program material mechanical behavior, as it allows the strength and three-dimensional organization of chemical bonds to be used as handles to manipulate how a material responds to external stress. DNA-grafted nanoparticles are a particularly promising building block for such hierarchically organized materials because of DNA's tunable and nucleobase sequence-specific complementary binding. Using nanoindentation, we show here that the programmability of oligonucleotide interactions allows the modulus of DNA-grafted nanoparticle superlattices to be easily tuned overly nearly 2 orders of magnitude. Additionally, we demonstrate that alterations to the supramolecular bond strength between particles can alter how a lattice deforms under applied mechanical force. As a result, the superlattices can be programmed either to reorganize their internal structures to dissipate mechanical energy or to completely recover their initial structure upon relaxation, independently of how the particles are arranged in 3D space. These behaviors are subsequently explained as a function of the hierarchical structure of the DNA-guided assemblies by using a simple truss-structure model. Altering the supramolecular DNA connections between particles therefore provides a simple and rational means of dictating different aspects of material mechanical response to produce tailorable properties that are not typically observed in conventional bulk materials. Ultimately, these studies enable control over the deformation behavior of future DNA-assembled nanomaterials and provide evidence that supramolecular chemistry is an effective tool in controlling the mechanical properties of nanomaterials as a function of their hierarchical design.