Effect of polyampholyte net charge on complex coacervation between polyampholytes and inorganic polyoxometalate giant anions

Abstract

The effect of net charge of zwitterionic polymers on the phase behavior and viscoelastic properties of hybrid polyampholyte–polyoxometalate (POM) complexes in salted aqueous solutions is investigated with polyampholyte copolymers consisting of both positively and negatively charged monomers. Zwitterionic polyampholytes of varied net charge, abbreviated as PA_xM_y, are synthesized by varying the feeding molar ratio of negatively charged 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) to positively charged [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) monomers in aqueous solution. The coacervate formation between PA_xM_y and inorganic anionic metatungstate POM ({W₁₂}) in LiCl added aqueous solutions can be enhanced by increasing the molar fraction of positively charged MAPTAC monomer and LiCl concentration. The salt-broadened coacervation, clearly distinct from the salt-suppressed one between oppositely charged polyelectrolytes, suggests the account of zwitterion-anion pairing for PA_xM_y–{W₁₂} coacervate formation due to stronger binding of multivalent {W₁₂} giant ions with PA_xM_y than simple ions. Importantly, as AMPS or MAPTAC monomer fraction in polyampholytes is varied by merely ±5% from the effective net neutral case, the viscoelasticity of PA_xM_y–{W₁₂} coacervates can be modified by 4–5 folds, suggesting a new tuning parameter to fine control the macroionic interactions and material properties of biomimetic complex coacervates.