Monte Carlo simulations of weak polyampholyte microgels: pH-dependence of conformation and ionization.

We performed Metropolis Monte Carlo simulations to investigate the impact of varying acid and base dissociation constants on the pH-dependent ionization and conformation of weak polyampholyte microgels under salt-free conditions and under explicit consideration of the chemical ionization equilibria of the acidic and basic groups and their electrostatic interaction. Irrespective of their relative acid and base dissociation constant, all of the microgels undergo a pH-dependent charge reversal from positive to negative with a neutral charge at the isoelectric point. This charge reversal is accompanied by a U-shaped swelling transition of the microgels with a minimum of their size at the point of charge neutrality. The width of the U-shaped swelling transition, however, is found to depend on the chosen relative acid and base dissociation constants through which the extent of the favorable electrostatic intramolecular interaction of the ionized acidic and basic groups is altered. The pH-dependent swelling transition of the microgels is found to become broader, the stronger the intramolecular electrostatic interaction of the oppositely charged ionized species is. In addition, the intramolecular charge compensation of the acidic and basic groups of the microgels allows their counterions to abandon the microgel and the associated gain in translational entropy further amplifies the broadening of the pH-dependent swelling transition. The analysis of the radial ionization profiles of the acidic and basic groups of the differently composed microgels reveals a variety of radial ionization patterns with a dependence on the overall charge of the microgels.