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Biomimetic self-templating supramolecular structures

Abstract

In nature, helical macromolecules such as collagen, chitin and cellulose are critical to the morphogenesis and functionality of various hierarchically structured materials1,2,3. During tissue formation, these chiral macromolecules are secreted and undergo self-templating assembly, a process whereby multiple kinetic factors influence the assembly of the incoming building blocks to produce non-equilibrium structures1,4. A single macromolecule can form diverse functional structures when self-templated under different conditions. Collagen type I, for instance, forms transparent corneal tissues from orthogonally aligned nematic fibres5, distinctively coloured skin tissues from cholesteric phase fibre bundles6,7, and mineralized tissues from hierarchically organized fibres8. Nature’s self-templated materials surpass the functional and structural complexity achievable by current top-down and bottom-up fabrication methods9,10,11,12. However, self-templating has not been thoroughly explored for engineering synthetic materials. Here we demonstrate the biomimetic, self-templating assembly of chiral colloidal particles (M13 phage) into functional materials. A single-step process produces long-range-ordered, supramolecular films showing multiple levels of hierarchical organization and helical twist. Three distinct supramolecular structures are created by this approach: nematic orthogonal twists, cholesteric helical ribbons and smectic helicolidal nanofilaments. Both chiral liquid crystalline phase transitions and competing interfacial forces at the interface are found to be critical factors in determining the morphology of the templated structures during assembly. The resulting materials show distinctive optical and photonic properties, functioning as chiral reflector/filters and structural colour matrices. In addition, M13 phages with genetically incorporated bioactive peptide ligands direct both soft and hard tissue growth in a hierarchically organized manner. Our assembly approach provides insight into the complexities of hierarchical assembly in nature and could be expanded to other chiral molecules to engineer sophisticated functional helical-twisted structures.

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Figure 1: Schematic diagram of the phage-based self-templating process.
Figure 2: Self-templated helical supramolecular structures.
Figure 3: Optical properties of the self-templated supramolecular structures.
Figure 4: Growth of biomimetic soft and hard tissue on the self-templated structures.

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Acknowledgements

This work was supported by the National Science Foundation Early Career Development Award (DMR-0747713), the Center of Integrated Nanomechanical Systems (COINS) of the National Science Foundation (grant no. EEC-0832819), the National Institute of Dental and Craniofacial Research (R21DE018360), the Defense Advanced Research Projects Agency (DARPA) program on Tip-Based Nanofabrication (TBN), start-up funds from the Nanoscience and Nanotechnology Institute at the University of California, Berkeley, the Laboratory Directed Research and Development fund from the Lawrence Berkeley National Laboratory, and the Korea Research Foundation Grant (to W.J.C.) funded by the Korean government (MOEHRD) (KRF-2006-352-D00048).

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Contributions

W.J.C. and S.W.L. designed the project. W.J.C. developed and optimized the phage assembly method. W.J.C., J.W.O., K.K., B.Y.L., J.M., A.H. and S.W.L. performed optical characterization and analysis. W.J.C. performed the tissue culture and biomineralization experiment. W.J.C., B.Y.L. and E.W. performed mechanical property measurement and analysed the data. J.M. programmed the pulling software. W.J.C., E.W. and S.W.L. wrote the manuscript and coordinated contributions by other authors.

Corresponding author

Correspondence to Seung-Wuk Lee.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Methods and Data, which include a table and figures A- E with legends, Supplementary Figures 1 -16, a legend for Supplementary Movie 1 and Supplementary References. (PDF 3975 kb)

Supplementary Movie 1

This movie shows the self-templating film deposition process as a gold-coated silicon substrate is pulled out of a 1 mg/mL phage suspension (see Supplementary Information file for full legend). (MOV 24278 kb)

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Chung, WJ., Oh, JW., Kwak, K. et al. Biomimetic self-templating supramolecular structures. Nature 478, 364–368 (2011). https://doi.org/10.1038/nature10513

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