Temperature-sensitive nanogels in the presence of salt: explicit coarse-grained simulations

In this work, coarse-grained simulations of two charged thermo-shrinking nanogels (with degrees of ionization of 0.125 and 0.250) in the presence of 1:1 and 3:1 electrolytes have been explicitly performed through the bead-spring model of polyelectrolyte. In a first set of simulations, salt concentrations for 1:1 and 3:1 electrolytes ranged from 1 to 100 mM and from 0.167 to 16.7 mM, respectively, whereas temperature remained fixed at a value for which hydrophobic forces were negligible in our case (288 K). The sizes of swollen nanogels are smaller when trivalent cations are present, but they do not change significantly in the range of concentrations of 3:1 electrolyte studied here. It should be also stressed that trivalent cations neutralize the nanogel charge more efficiently. According to these results the electrostatic repulsion plays an important role. In a second set of simulations, the temperature varied from 288 to 333 K to study the effect of salt on the thermal response when hydrophobic forces are not negligible. For the nanogels with the lowest degree of ionization, the behavior of the radius with increasing the temperature can be described by a sigmoid function, which shifts towards lower temperatures in the presence of salt. This shift is more clearly observed for trivalent cations, even at low concentrations. For the nanogels with the highest degree of ionization, the effect of additional electrolyte is also noticeable. In this case, hydrophobic forces are not the only responsible for their shrinkage in the presence of trivalent cations. The surface electrostatic potential and the concentration of salt cations inside the nanogel have been computed from simulations and a modified Poisson-Boltzmann (PB) cell model. The thermosensitivity in size have certain influence on the sensitivity of these properties to temperature changes. The rich behavior of the surface electrostatic potential and the uptake of salt cations are successfully predicted by the modified PB cell model proposed (at least qualitatively). Particularly, the model is able to predict how the retention of salt cations depends on their charge and the ionic valence when nanogels shrink.