Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Reconfigurable self-assembly through chiral control of interfacial tension

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.

This is a preview of subscription content

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

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.

References

  1. Pasteur, L. On the relations that can exist between crystalline form, and chemical composition and the sense of rotary polarization. Ann. Chim. Phys. 24, 442–459 (1848)

    Google Scholar 

  2. Hirokawa, N., Tanaka, Y., Okada, Y. & Takeda, S. Nodal flow and the generation of left-right asymmetry. Cell 125, 33–45 (2006)

    CAS  Article  Google Scholar 

  3. Harris, A. B., Kamien, R. D. & Lubensky, T. C. Molecular chirality and chiral parameters. Rev. Mod. Phys. 71, 1745–1757 (1999)

    ADS  CAS  Article  Google Scholar 

  4. Oda, R., Huc, I., Schmutz, M., Candau, S. J. & MacKintosh, F. C. Tuning bilayer twist using chiral counterions. Nature 399, 566–569 (1999)

    ADS  CAS  Article  Google Scholar 

  5. Aggeli, A. et al. Hierarchical self-assembly of chiral rod-like molecules as a model for peptide beta-sheet tapes, ribbons, fibrils, and fibers. Proc. Natl Acad. Sci. USA 98, 11857–11862 (2001)

    ADS  CAS  Article  Google Scholar 

  6. Kamien, R. D. & Selinger, J. V. Order and frustration in chiral liquid crystals. J. Phys. Condens. Matter 13, R1–R22 (2001)

    ADS  CAS  Article  Google Scholar 

  7. de Gennes, P. G. An anology between superconductors and smectics A. Solid State Commun. 88, 1039–1042 (1993)

    ADS  Article  Google Scholar 

  8. Renn, S. R. & Lubensky, T. C. Abrikosov dislocation lattice in a model of the cholesteric to smectic-A transition. Phys. Rev. A 38, 2132–2147 (1988)

    ADS  CAS  Article  Google Scholar 

  9. Matsumoto, E. A., Alexander, G. P. & Kamien, R. D. Helical nanofilaments and the high chirality limit of smectics A . Phys. Rev. Lett. 103, 257804 (2009)

    ADS  Article  Google Scholar 

  10. Hough, L. E. et al. Helical nanofilament phases. Science 325, 456–460 (2009)

    ADS  CAS  Article  Google Scholar 

  11. Barry, E. & Dogic, Z. Entropy driven self-assembly of nonamphiphilic colloidal membranes. Proc. Natl Acad. Sci. USA 107, 10348–10353 (2010)

    ADS  CAS  Article  Google Scholar 

  12. Safran, S. Statistical Thermodynamics of Surfaces, Interfaces, and Membranes 79–85 (Addison Wesley, 1994)

    MATH  Google Scholar 

  13. Barry, E., Beller, D. & Dogic, Z. A model liquid crystalline system based on rodlike viruses with variable chirality and persistence length. Soft Matter 5, 2563–2570 (2009)

    CAS  Google Scholar 

  14. Baumgart, T., Hess, S. T. & Webb, W. W. Imaging coexisting fluid domains in biomembrane models coupling curvature and line tension. Nature 425, 821–824 (2003)

    ADS  CAS  Article  Google Scholar 

  15. Honerkamp-Smith, A. R. et al. Line tensions, correlation lengths, and critical exponents in lipid membranes near critical points. Biophys. J. 95, 236–246 (2008)

    CAS  Article  Google Scholar 

  16. Lee, K. Y. C. & McConnell, H. M. Quantitized symmetry of liquid monolayer domains. J. Phys. Chem. 97, 9532–9539 (1993)

    CAS  Article  Google Scholar 

  17. Dogic, Z. & Fraden, S. Cholesteric phase in virus suspensions. Langmuir 16, 7820–7824 (2000)

    CAS  Article  Google Scholar 

  18. Oldenbourg, R. & Mei, G. New polarized light microscope with precision universal compensator. J. Microsc. 180, 140–147 (1995)

    CAS  Article  Google Scholar 

  19. Barry, E., Dogic, Z., Meyer, R. B., Pelcovits, R. A. & Oldenbourg, R. Direct measurement of the twist penetration length in a single smectic a layer of colloidal virus particles. J. Phys. Chem. B 113, 3910–3913 (2009)

    CAS  Article  Google Scholar 

  20. Oldenbourg, R. Polarized light field microscopy: an analytical method using a microlens array to simultaneously capture both conoscopic and orthoscopic views of birefringent objects. J. Microsc. 231, 419–432 (2008)

    MathSciNet  CAS  Article  Google Scholar 

  21. Aarts, D. G. A. L., Schmidt, M. & Lekkerkerker, H. N. W. Direct visual observation of thermal capillary waves. Science 304, 847–850 (2004)

    ADS  CAS  Article  Google Scholar 

  22. Fradin, C. et al. Reduction in the surface energy of liquid interfaces at short length scales. Nature 403, 871–874 (2000)

    ADS  CAS  Article  Google Scholar 

  23. Pelcovits, R. A. & Meyer, R. B. Twist penetration in single-layer smectic A discs of colloidal virus particles. Liq. Cryst. 36, 1157–1160 (2009)

    CAS  Article  Google Scholar 

  24. Kaplan, C. N., Tu, H., Pelcovits, R. A. & Meyer, R. B. Theory of depletion-induced phase transition from chiral smectic-A twisted ribbons to semi-infinite flat membranes. Phys. Rev. E 82, 021701 (2010)

    ADS  Article  Google Scholar 

  25. Srivastava, S. et al. Light-controlled self-assembly of semiconductor nanoparticles into twisted ribbons. Science 327, 1355–1359 (2010)

    ADS  CAS  Article  Google Scholar 

  26. Chung, W. J. et al. Biomimetic self-templating supramolecular structures. Nature 478, 364–368 (2011)

    ADS  CAS  Article  Google Scholar 

  27. Grason, G. M. & Bruinsma, R. F. Chirality and equilibrium biopolymer bundles. Phys. Rev. Lett. 99, 098101 (2007)

    ADS  Article  Google Scholar 

  28. Claessens, M., Semmrich, C., Ramos, L. & Bausch, A. R. Helical twist controls the thickness of F-actin bundles. Proc. Natl Acad. Sci. USA 105, 8819–8822 (2008)

    ADS  CAS  Article  Google Scholar 

  29. Nguyen, T. D. & Glotzer, S. C. Switchable helical structures formed by the hierarchical self-assembly of laterally tethered nanorods. Small 5, 2092–2098 (2009)

    CAS  Article  Google Scholar 

  30. Nguyen, T. D. & Glotzer, S. C. Reconfigurable assemblies of shape-changing nanorods. ACS Nano 4, 2585–2594 (2010)

    CAS  Article  Google Scholar 

  31. Maniatis, T., Sambrook, J. & Fritsch, E. Molecular Cloning Ch. 3. (1989)

  32. Lettinga, M. P., Barry, E. & Dogic, Z. Self-diffusion of rod-like viruses in the nematic phase. Europhys. Lett. 71, 692–698 (2005)

    ADS  CAS  Article  Google Scholar 

  33. Tang, J. X. & Fraden, S. Nonmonotonic temperature dependence of the flexibility of bacteriophage fd. Biopolymers 39, 13–22 (1996)

    CAS  Article  Google Scholar 

  34. Lau, A. W. C., Prasad, A. & Dogic, Z. Condensation of isolated semi-flexible filaments driven by depletion interactions. Europhys. Lett. 87, 48006 (2009)

    ADS  Article  Google Scholar 

  35. Purdy, K. R. et al. Measuring the nematic order of suspensions of colloidal fd virus by X-ray diffraction and optical birefringence. Phys. Rev. E 67, 031708 (2003)

    ADS  Article  Google Scholar 

  36. Mastronarde, D. N. Automated electron microscope tomography using robust prediction of specimen movements. J. Struct. Biol. 152, 36–51 (2005)

    Article  Google Scholar 

  37. Kremer, J. R., Mastronarde, D. N. & McIntosh, J. R. Computer visualization of three-dimensional image data using IMOD. J. Struct. Biol. 116, 71–76 (1996)

    CAS  Article  Google Scholar 

  38. Yang, Y., Barry, E., Dogic, Z. & Hagan, M. F. Self-assembly of 2D membranes from mixtures of hard rods and depleting polymers. Soft Matter 8, 707–714 (2012)

    ADS  CAS  Article  Google Scholar 

Download references

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.

Author information

Authors and Affiliations

Authors

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.

Ethics declarations

Competing interests

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)

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature10769

Further reading

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing