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

Nature Materials volume 13, pages 1055–1062 (2014)Cite this article

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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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Figure 1: A biomimetic modular polymer is synthesized and studied at single-molecule and bulk levels, which are directly correlated here.
Figure 2: SMFS pulling experiments show robust saw-tooth patterns in force spectra and the Bell–Evans fit derives the dissociative kinetics.
Figure 3: Cyclic SMFS experiments demonstrate re-folding of modules and the fit of rejoining forces derives the associative kinetics.
Figure 4: Mechanical characterization of bulk SB-UPy-DCL material demonstrates high strength and toughness, and slow dynamic recovery of the properties.
Figure 5: The potential energy landscape constructed for SB-UPy-DCL unfolding based on SMFS data bridges the nanomechanical and emergent bulk properties.

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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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  1. Department of Chemistry, 1102 Natural Sciences 2, University of California, Irvine, California 92697-2025, USA

    Jaeyoon Chung, Aaron M. Kushner, Adam C. Weisman & Zhibin Guan

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  1. Jaeyoon Chung
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  2. Aaron M. Kushner
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Contributions

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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Correspondence to Zhibin Guan.

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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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