The Effect of Intramolecular Cross‐Linking on Polymer Interactions in Solution

Abstract The conformation of a polymer in a solvent is typically defined by the solvent quality, which is a consequence of the solvent and macromolecule's chemistry. Yet, additional factors can affect the polymer conformation, such as non‐covalent interactions to surfaces or other macromolecules, affecting the amount of polymer–solvent interactions. Herein, chemically folded polymers with protein‐like architectures are studied and compared to their unfolded linear precursor in good solvents using rheology measurements. The current research reveals that permanent folding by intramolecular chemical cross‐linking limits the chain mobility and therefore causes a reduction in polymer–solvent interactions, making a good solvent become theta. This change not only affects the “solvent quality” but also leads to a change in particle–particle interactions as a function of concentration. These findings provide crucial insight into the effects of intramolecular cross‐links on macromolecule solubility and self‐assembly, which are critical for mimicking structurally similar biological materials.