Counterion-Mediated Assembly of Spherical Nucleic Acid-Au Nanoparticle Conjugates (SNA-AuNPs)

Controlled crystallization of colloids from solution has been a goal of material scientists for decades. Recently, nucleic acid functionalized spherical Au nanoparticles (SNA-AuNPs) have been programmed to assemble in a wide variety of crystal structures. In this approach, the assembly is driven by Watson-Crick hybridization between DNAs coating the AuNPs. Here, we show that counterions can induce ordered assembly of SNA-AuNPs in bulk solutions, even in the absence of base pairing interactions. The electrostatics-driven assembly of spherical nucleic acid-Au nanoparticle conjugates (SNA-AuNPs) is probed as a function of counterion concentration and counterion valency [$+$1 (Na$^{+})$ or $+$2 (Ca$^{2+})$] by \textit{in situ} solution X-ray scattering. Assemblies of AuNPs capped with single-stranded (ss-) or double-stranded (ds-) DNA are examined. SAXS reveals disordered (gas-like) $\to $ face-centered-cubic (FCC) $\to$ glass-like phase transitions with increasing solution ionic strength. These studies demonstrate how non-base-pairing interactions can be tuned to create crystalline assemblies of SNA-AuNPs. The dependence of the inter-SNA-AuNP interactions on counterion valency and stiffness of the DNA corona will be discussed.