Significance The use of biological enzyme catalysts could have huge ramifications for chemical industries. However, these enzymes are often inactive in nonbiological conditions, such as high temperatures, present in industrial settings. Here, we show that the enzyme PETase (polyethylene terephthalate [PET]), with potential application in plastic recycling, is stabilized at elevated temperature through complexation with random copolymers. We demonstrate this through simulations and experiments on different types of substrates. Our simulations also provide strategies for designing more enzymatically active complexes by altering polymer composition and enzyme charge distribution.

Nature harnesses the disorder of intrinsically disordered proteins to organize enzymes and biopolymers into membraneless organelles. The heterogeneous nature of synthetic random copolymers with charged, polar, and hydrophobic groups has been exploited to mimic intrinsically disordered proteins, forming complexes with enzymatically active proteins and delivering them into nonbiological environments. Here, the properties of polyelectrolyte complexes composed of two random copolymer polyelectrolytes are studied experimentally and via simulation with the aim of exploiting such complexes for segregating organic molecules from water. The anionic polyelectrolyte contains hydrophilic and hydrophobic side chains and forms self-assembled hydrophobic domains. The cationic polymer is a high-molecular-weight copolymer of hydrophilic and charged side groups and acts as a flocculant. We find that the polyelectrolyte complexes obtained with this anionic and cationic random copolymer system are capable of absorbing small cationic, anionic, and hydrophobic organic molecules, including perfluorooctanoic acid, a compound of great environmental and toxicologic concern. Importantly, these macroscopic complexes can be easily removed from water, thereby providing a simple approach for organic contaminant removal in aqueous media. MARTINI and coarse-grained molecular dynamics simulations explore how the microscale heterogeneity of these random copolymer complexes relates to their segregation functionality.

We investigate the usage of polyelectrolyte complex materials for water remediation purposes, specifically their ability to remove nanoplastics from water, on which there is currently little to no prior research. We demonstrate that oppositely charged random copolymers are effective at quantitatively removing nanoplastic contamination from aqueous solution. The mechanisms underlying this remediation ability are explored through computational simulations, with corroborating quartz crystal microbalance adsorption experiments. We find that hydrophobic nanostructures and interactions likely play an important role.