100th Anniversary of Macromolecular Science Viewpoint: Single-Molecule Studies of Synthetic Polymers.

Single polymer studies have revealed unexpected and heterogeneous dynamics among identical or seemingly similar macromolecules. In recent years, direct observation of single polymers has uncovered broad distributions in molecular behavior that play a key role in determining bulk properties. Early single polymer experiments focused primarily on biological macromolecules such as DNA, but recent advances in synthesis, imaging, and force spectroscopy have enabled broad exploration of chemically diverse polymer systems. In this Viewpoint, we discuss the recent study of synthetic polymers using single-molecule methods. In terms of polymer synthesis, direct observation of single chain polymerization has revealed heterogeneity in monomer insertion events at catalytic centers and decoupling of local and global growth kinetics. In terms of single polymer visualization, recent advances in super-resolution imaging, atomic force microscopy (AFM), and liquid-cell transmission electron microscopy (LC-TEM) can resolve structure and dynamics in single synthetic chains. Moreover, single synthetic polymers can be probed in the context of bulk material environments, including hydrogels, nanostructured polymers, and crystalline polymers. In each area, we highlight key challenges and exciting opportunities in using single polymer techniques to enhance our understanding of polymer science. Overall, the expanding versatility of single polymer methods will enable the molecular-scale design and fundamental understanding of a broad range of chemically diverse and functional polymeric materials.