Diffusiophoresis in Polymer and Nanoparticle Gradients

Diffusiophoresis is the movement of the colloidal particles in response to a concentration gradient and can be observed for both electrolyte (e.g., salt) and nonelectrolyte (e.g., glucose) solutes. Here, we investigated the diffusiophoretic behavior of polystyrene (PS-carboxylate surface) microparticles in nonadsorbing charged and uncharged solute gradients [sodium polystyrenesulfonate (NaPSS), polyethylene glycol (PEG), and nanoscale colloidal silica (SiO₂)] using a dead-end channel setup. We compared the diffusiophoretic motion in these gradient types with each other and to the case of using a monovalent salt gradient. In each of the nonadsorbing gradient systems (NaPSS, PEG, and SiO₂ nanoparticles), the PS particles migrated toward the lower solute concentration. The exclusion distance values (from the initial position) of particles were recorded within the dead-end channel, and it was found that an increase in solute concentration increases exclusion from the main channel. In the polyelectrolyte case, the motion of PS microparticles was reduced by the addition of a background salt due to reduced electrostatic interaction, whereas it remained constant when using the neutral polymer. Particle diffusiophoresis in gradients of polyelectrolytes (charged macromolecules) is quite similar to the behavior when using a PEG gradient (uncharged macromolecule) in the presence of a background electrolyte. Moreover, we observed PS microparticles under different concentrations and molecular weights of PEG gradients. By combining the simulations, we estimated the exclusion length, which was previously proposed to be the order of the polymer radius. Furthermore, the movement of PS microparticles was analyzed in the gradient of silica nanoparticles. The exclusion distance was higher in silica nanoparticle gradients compared to similar-size PEG gradients because silica nanoparticles are charged. The diffusiophoretic transport of the PS microparticles could be simulated by considering the interaction between the PS microparticles and silica nanoparticles.