Direct correlation of single-molecule properties with bulk mechanical performance for the biomimetic design of polymers.

Abstract

For rational design of advanced polymeric materials, it is critical to establish a clear mechanistic link between the molecular structure of a polymer and the emergent bulk mechanical properties. Despite progress towards this goal, it remains a major challenge to directly correlate the bulk mechanical performance to the nanomechanical properties of individual constituent macromolecules. Here, we show a direct correlation between the single-molecule nanomechanical properties of a biomimetic modular polymer and the mechanical characteristics of the resulting bulk material. The multi-cyclic single-molecule force spectroscopy (SMFS) data enabled quantitative derivation of the asymmetric potential energy profile of individual module rupture and re-folding, in which a steep dissociative pathway accounted for the high plateau modulus, while a shallow associative well explained the energy-dissipative hysteresis and dynamic, adaptive recovery. These results demonstrate the potential for SMFS to serve as a guide for future rational design of advanced multifunctional materials.