Electrolyte-Mediated Assembly of Charged Nanoparticles

Solutions at high salt concentrations are used to crystallize or segregate colloids, proteins and polyelectrolytes via an unknown mechanism referred to as ``salting-out''. Here, we show salting-out is a long-range interaction controlled by electrolyte concentration and nanoparticle charge density. Small-angle X-ray scattering (SAXS) shows that DNA-coated Au nanoparticles designed to prevent inter-particle assembly via Watson-Crick hybridization undergo ``gas'' to FCC to ``glass-like'' transitions with increasing NaCl or CaCl$_{\mathrm{2\thinspace }}$concentration. Simulations reveal that the crystallization is concomitant with inter-particle interactions changing from purely repulsive to a long-range potential well condition. Liquid-state theory explains this attraction as a sum of cohesive and depletion forces. Our work reveals the mechanism behind salting-out and suggests new routes for the successful crystallization of colloids and proteins using concentrated salts.