Synthesis of Raspberry-like Nanoparticles via Surface Grafting of Positively Charged Polyelectrolyte Brushes: Colloidal Stability and Surface Properties.

A method to synthesize stable, raspberry-like nanoparticles (NPs), using surface grafting of poly(glycidyl methacrylate) (PGMA) brushes on a polystyrene (PS) core with varying grafting densities, is reported. A two-step functionalization reaction of PGMA epoxide groups comprising an amination step first using ethylene diamine and then followed by a quaternization using glycidyltrimethylammonium chloride generates permanently and positively charged polyelectrolyte brushes, which result in both steric and electrostatic stabilization. The dispersion stability of the brush-bearing NPs is dramatically improved compared to that of the pristine PS core in salt solutions at ambient (25 °C) and elevated temperatures (60 °C). Additionally, the grafted polyelectrolyte chains undergo a reversible swelling in the presence of different ionic strength (IS) salts, which modulate the surface properties, including roughness, stiffness, and adhesion. An atomic force microscope under both dry and wet conditions was used to image conformational changes of the polyelectrolyte chains during the swelling and deswelling transitions as well as to probe the nanomechanical properties by analyzing the corresponding force-sample separation curves. The quaternized polyelectrolyte brushes undergo a conformational transition from a collapsed state to a swelled state in the osmotic brush (OB) regime triggered by the osmotic gradient of mobile ions to the interior of the polymer chain. At IS ∼ 1 M, the brushes contract and the globules reform (salted brush state) as evidenced by an increase in the surface roughness and a reduction in the adhesion of the brushes. Beyond IS ∼ 1 M, quartz crystal microbalance with dissipation monitoring measurements show that salt uptake continues to take place predominantly on the exterior surface of the brush since salt adsorption is not accompanied by a size increase as measured by dynamic light scattering. The study adds new insights into our understanding of the behavior of NPs bearing salt-responsive polyelectrolyte brushes with adaptive swelling thresholds that can ultimately modulate surface properties.