Atomic-Scale Imaging of Polymers and Precision Molecular Weight Analysis

Polymer design requires fine control over syntheses and a thorough understanding of their macromolecular structure. Herein, near-atomic level imaging of polymers is achieved, enabling the precise determination of one of the most important macromolecular characteristics: molecular weight. By judiciously designing and synthesizing different linear metal(loid)-rich homopolymers, subnanoscale polymer imaging is achieved through annular dark field-scanning transmission electron microscopy (ADF-STEM), owing to the incorporation of high Z atoms in the side chain of the monomeric units. The molecular weight of these polymers can be precisely determined by detecting and counting their metal(loid) atoms upon ADF-STEM imaging, at sample concentrations as low as 10 μg·mL^-1. Notably, a commonly used C, H, and O-containing polymer (i.e., poly(methyl acrylate)) that was thus far inaccessible at the atomic scale is derivatized to allow for subnano-level imaging, thus expanding the scope of our approach toward the atomic-level visualization of commodity polymers.