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.
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Acknowledgements
We acknowledge the financial support of the US Department of Energy, Division of Materials Sciences (DE-FG02-04ER46162) (J.C. for SMFS studies), and the National Science Foundation (DMR-1217651) (A.M.K. for bulk property studies). J.C. thanks Jason Bemis at Asylum Research of Oxford Instruments in Santa Barbara, California for assistance in the set-up of cyclic SMFS studies. We also thank the Materia Inc. for supplying the Grubbs second generation metathesis catalyst.
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Z.G. conceived the project; Z.G., A.M.K. and J.C. planned the experiments; J.C., A.M.K. and A.C.W. performed the experiments; J.C., A.M.K. and Z.G. analysed the data; and J.C., A.M.K. and Z.G. wrote the paper.
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Chung, J., Kushner, A., Weisman, A. et al. Direct correlation of single-molecule properties with bulk mechanical performance for the biomimetic design of polymers. Nature Mater 13, 1055–1062 (2014). https://doi.org/10.1038/nmat4090
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DOI: https://doi.org/10.1038/nmat4090
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