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.

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

In this study, we investigated the effect of pH on single weak acidic polyelectrolyte microgels under salt-free conditions with (i) varying microgel concentration, (ii) varying content of acidic groups and (iii) different crosslinking densities using Monte Carlo simulations under explicit consideration of the protonation/deprotonation reaction. We assessed both global properties, such as the degree of ionization, the degree of swelling and the counterion distribution, and local properties such as the radial network ionization profile and the ionization along the polymer chains as a function of pH. We found a pronounced suppression of the pH-dependent ionization of the microgels, as compared to the ideal titration behavior and a shift of the titration curve to a higher pH originating in the proximity of acidic groups in the microgel. In contrast to macroscopic gels, counterions can leave the microgel, resulting in an effective charge of the network, which hinders the ionization. A decreasing microgel concentration leads to an increased effective charge of the microgel and a more pronounced shift of the titration curve. The number of acidic groups showed only a weak effect on the ionization behavior of the microgels. For two different microgels with different crosslinking densities, similar scaling of the gel size was observed. A distinct transition from an uncharged and unswollen to a highly charged and expanded polymer network was observed for all investigated microgels. The degree of swelling mainly depends on the degree of ionization. An inhomogeneous distribution of the degree of ionization along the radial profile of the microgel was found.