Counting loops in sidechain-crosslinked polymers from elastic solids to single-chain nanoparticles

The vast differences in material properties accessible via crosslinking of sidechain-functionalized polymers are driven by topology. For example, vulcanized rubbery networks feature intermolecular connections and loop topologies of various orders while single-chain nanoparticles (SCNPs) are comprised, in principle, entirely of primary loops. Despite this fact, precise quantification of loops in sidechain crosslinked polymers has not been accomplished. Here, it is demonstrated that by introducing cleavable linkers and mass labels onto the pendant functional groups of reactive polymers, the number of primary loops in sidechain crosslinked materials ranging from rubbery networks (gels) to soluble SCNPs can be precisely quantified. This study sheds new light on the topology of sidechain-crosslinked networks, providing design principles for augmenting the properties of this industrially and academically important class of materials through topological control.