Size-Dependent Electrostatic Adsorption of Polymer-Grafted Gold Nanoparticles on Polyelectrolyte Brushes

Designing a functional surface that selectively adsorbs nanoparticles based on their size and shape is essential for developing an advanced adsorption-based, postsynthesis nanoparticle separation device. We demonstrate selective adsorption of larger nanoparticles from solution onto a polyelectrolyte brush by tuning the salt concentration. Specifically, a positively charged polyelectrolyte brush is created by converting pyridine groups of poly(2-vinylpyridine) to n-methylpyridinium groups using methyl iodide. The adsorption kinetics and thermodynamics of poly(ethylene glycol)-grafted, negatively charged gold nanoparticles (diameters of 12 and 20 nm) were monitored as a function of salt concentration. In a salt-free solution, the polyelectrolyte brush adsorbs gold nanoparticles of both sizes. As the salinity increases, the areal number density of adsorbed nanoparticles monotonically decreases and becomes negligible at high salinity. Interestingly, there is an intermediate range of salt concentrations (i.e., 15-20 mM of NaCl) where the decrease in nanoparticle adsorption is more pronounced for smaller particles, leading to size-selective adsorption of the larger nanoparticles. As a further demonstration of selectivity, the polyelectrolyte brush is immersed in a binary mixture of 12 and 20 nm nanoparticles and found to selectively capture larger particles with ∼90% selectivity. In addition, the size distribution of as-synthesized gold nanoparticles, with an average diameter of 12 nm, was reduced by selectively removing larger particles by exposing the solution to polyelectrolyte brush surfaces. This study demonstrates the potential of a polyelectrolyte brush separation device to remove larger nanoparticles by controlling electrostatic interactions between polymer brushes and particles.