Ionic strength dependent forces between end-grafted Poly(sulfobetaine) films and mica.

The molecular surface properties of zwitterionic polymer coatings are central to their ultra-low fouling properties and effectiveness as steric stabilizers in concentrated salt solutions. Here, Surface Force Apparatus measurements quantified the molecular forces between end-grafted poly(sulfobetaine) methacrylate thin films and mica, as a function of the chain grafting density and ionic strength. These results demonstrate that, at the ionic strengths considered, end-grafted poly(sulfobetaine) films can be described by models for polymers in good solvent. Parameters determined from data fits to the Milner-Witten-Cates or Dolan and Edwards models for dense or dilute chains, respectively, varied with ionic strength, in ways that reflect poly(sulfobetaine) swelling and the increased excluded volume strength of chain segments. These force measurements provide new insight into how polymer coverage and salt cooperate to regulate repulsive poly(sulfobetaine) steric barriers. These findings have implications for the design of grafted poly(sulfobetaine) as colloidal stabilizers or nonfouling surface coatings.

Sequence and entropy-based control of complex coacervates.

Biomacromolecules rely on the precise placement of monomers to encode information for structure, function, and physiology. Efforts to emulate this complexity via the synthetic control of chemical sequence in polymers are finding success; however, there is little understanding of how to translate monomer sequence to physical material properties. Here we establish design rules for implementing this sequence-control in materials known as complex coacervates. These materials are formed by the associative phase separation of oppositely charged polyelectrolytes into polyelectrolyte dense (coacervate) and polyelectrolyte dilute (supernatant) phases. We demonstrate that patterns of charges can profoundly affect the charge-charge associations that drive this process. Furthermore, we establish the physical origin of this pattern-dependent interaction: there is a nuanced combination of structural changes in the dense coacervate phase and a 1D confinement of counterions due to patterns along polymers in the supernatant phase.