Controlling Exchange Pathways in Dynamic Supramolecular Polymers by Controlling Defects

Supramolecular fibers composed of monomers that self-assemble directionally via noncovalent interactions are ubiquitous in nature, and great interest chemistry. In these structures, the constitutive continuously exchange in-and-out assembly according to a well-defined supramolecular equilibrium. However, unraveling pathways their molecular determinants constitutes nontrivial challenge. Here, we combine coarse-grained modeling, enhanced sampling, machine learning investigate key factors controlling monomer synthetic polymers having an intrinsic dynamic behavior. We demonstrate how competition directional vs. nondirectional between controls creation/annihilation defects polymers, from where proceeds. This determines pathway, dictating whether fiber statistically swaps tips or all along its length. Finally, thanks generality, our models allow investigation approaches control assemblies.