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Reconfigurable self-assembly through chiral control of interfacial tension

Nature volume 481, pages 348–351 (2012)Cite this article

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Abstract

From determining the optical properties of simple molecular crystals to establishing the preferred handedness in highly complex vertebrates, molecular chirality profoundly influences the structural, mechanical and optical properties of both synthetic and biological matter on macroscopic length scales1,2. In soft materials such as amphiphilic lipids and liquid crystals, the competition between local chiral interactions and global constraints imposed by the geometry of the self-assembled structures leads to frustration and the assembly of unique materials3,4,5,6. An example of particular interest is smectic liquid crystals, where the two-dimensional layered geometry cannot support twist and chirality is consequently expelled to the edges in a manner analogous to the expulsion of a magnetic field from superconductors7,8,9,10. Here we demonstrate a consequence of this geometric frustration that leads to a new design principle for the assembly of chiral molecules. Using a model system of colloidal membranes11, we show that molecular chirality can control the interfacial tension, an important property of multi-component mixtures. This suggests an analogy between chiral twist, which is expelled to the edges of two-dimensional membranes, and amphiphilic surfactants, which are expelled to oil–water interfaces12. As with surfactants, chiral control of interfacial tension drives the formation of many polymorphic assemblages such as twisted ribbons with linear and circular topologies, starfish membranes, and double and triple helices. Tuning molecular chirality in situ allows dynamical control of line tension, which powers polymorphic transitions between various chiral structures. These findings outline a general strategy for the assembly of reconfigurable chiral materials that can easily be moved, stretched, attached to one another and transformed between multiple conformational states, thus allowing precise assembly and nanosculpting of highly dynamical and designable materials with complex topologies.

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Figure 1: Edge structure of membranes assembled from an achiral mixture of wild-type and Tyr21Met fd phages.
Figure 2: Chiral control of effective line tension, γeff.
Figure 3: Transition of a 2D disk into 1D twisted ribbons.
Figure 4: Hierarchical self-assembly: from isolated viruses and metastable disks to singly and doubly twisted ribbons.

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Acknowledgements

This work was supported by the US National Science Foundation (NSF-MRSEC-0820492, NSF-DMR-0955776, NSF-MRI-0923057, NSF-CMMI-1068566) and the Petroleum Research Fund (ACS-PRF 50558-DNI7). We acknowledge use of the Brandeis MRSEC optical microscopy facility.

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Authors and Affiliations

  1. The Martin Fisher School of Physics, Brandeis University, 415 South Street, Waltham, Massachusetts 02454, USA ,

    Thomas Gibaud, Edward Barry, Mark J. Zakhary, Mir Henglin, Andrew Ward, Yasheng Yang, Michael F. Hagan, Robert B. Meyer & Zvonimir Dogic

  2. Department of Biology, Brandeis University, 415 South Street, Waltham, Massachusetts 02454, USA,

    Cristina Berciu & Daniela Nicastro

  3. Marine Biological Laboratory, 7 MBL Street, Woods Hole, 02543, Massachusetts, USA

    Rudolf Oldenbourg

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Contributions

T.G., E.B., M.J.Z., R.B.M. and Z.D. designed the experiments and interpreted the results. T.G., E.B. and M.J.Z. performed the experiments. A.W. performed the optical trapping experiments. E.B., C.B. and D.N. performed the electron microscopy imaging. M.H. performed the experiments on mutant viruses. R.O. performed the LC-PolScope imaging. Y.Y. and M.F.H. designed and performed the computer simulations. T.G., E.B., M.J.Z. and Z.D. wrote the manuscript.

Corresponding author

Correspondence to Zvonimir Dogic.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

The file contains Supplementary Figures 1-9 with legends and full legends for Supplementary Movies 1-5. (PDF 10986 kb)

Supplementary Movie 1

This movie shows the reversible transition of a 2D colloidal membrane composed of fd viruses into several connected 1D twisted ribbons, induced by increasing the strength of chiral interactions between the constituent virus particles. The duration of the movie is 11.9 minutes. (MOV 8867 kb)

Supplementary Movie 2

The movie shows real-time composite phase contrast/fluorescence video of a 1D twisted ribbon reveals the dynamics of individual fluorescently labeled viruses within the ribbon. As the rods diffuse through the structure, their apparent shape changes from circular spots to elongated rods, indicating twisting. (MOV 736 kb)

Supplementary Movie 3

This movie depicts the reversible transition from 2D membranes to a 1D twisted ribbon by the application of a stretching force imparted by optical tweezers. (MOV 4223 kb)

Supplementary Movie 4

This movie illustrates the transition of a single 1D twisted ribbon into a 2D membrane by decreasing the strength of chiral interactions between the viruses. (MOV 3412 kb)

Supplementary Movie 5

The movie shows as in movie 1, a 2D membrane is transitioned into several twisted ribbons. In this movie, two of the formed ribbons anneal, altering the structure's topology and preventing the complete reformation of the 2D membrane upon reversing the transition. The duration of the movie is 14.4 minutes. (MOV 3296 kb)

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Gibaud, T., Barry, E., Zakhary, M. et al. Reconfigurable self-assembly through chiral control of interfacial tension. Nature 481, 348–351 (2012). https://doi.org/10.1038/nature10769

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