Guanidinium Can Break and Form Strongly Associating Ion Complexes

Guanidinium is one of nature's strongest denaturants and is also a motif that appears in several interfacial contexts such as the RGD sequence involved in cell adhesion, cell penetrating peptides, and antimicrobial molecules. It is important to quantify the origin of guanidinium's ion-specific interactions so that its unique behavior may be exploited in synthetic applications. The present work demonstrates that guanidinium ions can both break and form strongly associating ion complexes in a context-dependent way. These insights into guanidinium's behavior are elucidated using polyelectrolyte complexes (PECs), where interpolymer ion pairs between oppositely charged polymers play an important role in determining material stability. Different polycation-polyanion combinations can span a large range of association affinities, where more strongly associating complexes can remain insoluble in concentrated salt solutions and in extreme pH conditions. This high stability is desirable in several application contexts for PECs, but also renders them challenging to process and, therefore, to study since they cannot be dissolved into polymer solutions. Here we demonstrate that guanidinium salts are very effective in dissolving the poly(styrenesulfonate)/poly(allylamine) (PSS:PAH) complex, which has one of the highest reported polycation-polyanion association affinities. We also demonstrate the importance of charge identity in complexation phenomena by functionalizing guanidinium directly into poly(allylamine), resulting in a complex that remains stable under highly denaturing conditions. The model system of PSS:PAH is used to glean insights into guanidinium's denaturing activity, as well as to broadly comment on the nature of ion-specific interactions in charged macromolecules.