Revolving supramolecular chiral structures powered by light in nanomotor-doped liquid crystals

Abstract

Molecular machines operated by light have been recently shown to be able to produce oriented motion at the molecular scale1,2 as well as do macroscopic work when embedded in supramolecular structures3,4,5. However, any supramolecular movement irremediably ceases as soon as the concentration of the interconverting molecular motors or switches reaches a photo-stationary state6,7. To circumvent this limitation, researchers have typically relied on establishing oscillating illumination conditions—either by modulating the source intensity8,9 or by using bespoke illumination arrangements10,11,12,13. In contrast, here we report a supramolecular system in which the emergence of oscillating patterns is encoded at the molecular level. Our system comprises chiral liquid crystal structures that revolve continuously when illuminated, under the action of embedded light-driven molecular motors. The rotation at the supramolecular level is sustained by the diffusion of the motors away from a localized illumination area. Above a critical irradiation power, we observe a spontaneous symmetry breaking that dictates the directionality of the supramolecular rotation. The interplay between the twist of the supramolecular structure and the diffusion14 of the chiral molecular motors creates continuous, regular and unidirectional rotation of the liquid crystal structure under non-equilibrium conditions.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Motor-doped liquid crystals winding under irradiation, and associated chiral structures.
Fig. 2: Light-driven chiral structures revolving unidirectionally
Fig. 3: Universal character of the revolving chiral structures.
Fig. 4: Helix inversion promotes spatial confinement, and thus preserves the integrity of the revolving patterns.
Fig. 5: Orbital transport of cargo.

References

  1. 1.

    Balzani, V., Credi, A. & Venturi, M. Light powered molecular machines. Chem. Soc. Rev. 38, 1542–1550 (2009).

    Article  Google Scholar 

  2. 2.

    Kassem, S. et al. Artificial molecular motors. Chem. Soc. Rev. 46, 2592–2621 (2017).

    Article  Google Scholar 

  3. 3.

    Browne, W. R. & Feringa, B. L . Making molecular machines work. Nat. Nanotech. 1, 25–35 (2006).

    Article  Google Scholar 

  4. 4.

    Chen, J. et al. Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors. Nat. Chem. https://doi.org/10.1038/nchem.2887 (2017)

  5. 5.

    Van Leeuwen, T., Lubbe, A. S., Stacko, P., Wezenberg, S. J. & Feringa, B. L. Dynamic control of function by light-driven molecular motors. Nat. Rev. Chem. 1, 0096 (2017).

    Article  Google Scholar 

  6. 6.

    Eelkema, R. et al. Molecular machines: Nanomotor rotates microscale objects. Nature 440, 163 (2006).

    Article  Google Scholar 

  7. 7.

    Li, Q. et al. Macroscopic contraction of a gel induced by the integrated motion of light-driven molecular motors. Nat. Nanotech. 10, 161–165 (2015).

    Article  Google Scholar 

  8. 8.

    Foy, J. T. et al. Dual-light control of nanomachines that integrate motor and modulator subunits. Nat. Nanotech. 12, 540–545 (2017).

    Article  Google Scholar 

  9. 9.

    Yamada, M. et al. Photomobile polymer materials: Towards light-driven plastic motors. Angew. Chem. Int. Ed. 47, 4986–4988 (2008).

    Article  Google Scholar 

  10. 10.

    Gelebart, A. H. et al. Making waves in a photoactive polymer film. Nature 546, 632–636 (2017).

    Article  Google Scholar 

  11. 11.

    White, T. J. et al. A high frequency photodriven polymer oscillator. Soft Matter 4, 1796–1798 (2008).

    Article  Google Scholar 

  12. 12.

    Tabe, Y. et al. Photo-induced travelling waves in condensed Langmuir monolayers. New J. Phys. 5, 65.1–65.11 (2011).

    Google Scholar 

  13. 13.

    Martinez, A. & Smalyukh, I. I. Light-driven dynamic Archimedes spirals and periodic oscillatory patterns of topological solitons in anisotropic soft matter. Opt. Express 23, 4591–4604 (2015).

    Article  Google Scholar 

  14. 14.

    Epstein, I. R. & Xu, B. Reaction–diffusion processes at the nano and microscales. Nat. Nanotech. 11, 312–319 (2016).

    Article  Google Scholar 

  15. 15.

    Zeldovich, B. Y. & Tabiryan, N. V. Fréedericksz transition in cholesteric liquid crystal without external fields. JETP Lett. 34, 406–408 (1981).

    Google Scholar 

  16. 16.

    Haas, W. E. L. & Adams, J. E. Electrically variable diffraction in spherulitic liquid crystals. Appl. Phys. Lett. 25, 263–264 (1974).

    Article  Google Scholar 

  17. 17.

    Smalyukh, I. I. et al. Three-dimensional structure and multistable optical switching of triple-twisted particle-like excitations in anisotropic fluids. Nat. Mater. 9, 139–145 (2010).

    Article  Google Scholar 

  18. 18.

    Ackerman, P. J. et al. Two-dimensional skyrmions and other solitonic structures in confinement-frustrated chiral nematics. Phys. Rev. E 90, 012505 (2014).

    Article  Google Scholar 

  19. 19.

    Loussert, C. et al. Subnanowatt opto-molecular generation of localized defects in chiral liquid crystals. Adv. Mater. 26, 4242–4246 (2014).

    Article  Google Scholar 

  20. 20.

    Vicario, J., Walko, M., Meetsma, A. & Feringa, B. L. J. Am. Chem. Soc. 128, 5127–5135 (2006).

    Article  Google Scholar 

  21. 21.

    Pumpa, M. & Cichos, F. Slow single-molecule diffusion in liquid crystals. J. Phys. Chem. B 116, 14487–14493 (2012).

    Article  Google Scholar 

  22. 22.

    Galstian, T. & Allahverdyan, K. Molecular self-assemblies might discriminate the diffusion of chiral molecules. Soft Matter 11, 4167–4172 (2015).

    Article  Google Scholar 

  23. 23.

    Jiang, J. & Yang, D. -K. Chirality differentiation by diffusion in chiral nematic liquid crystals. Phys. Rev. Appl. 7, 014014 (2017).

    Article  Google Scholar 

  24. 24.

    Morrow, S. M., Bissette, A. J. & Fletcher, S. P. Transmission of chirality through space and across length scales. Nat. Nanotech. 12, 410–419 (2017).

    Article  Google Scholar 

  25. 25.

    Santamato, E. et al. Collective rotation of molecules driven by the angular momentum of light in a nematic film. Phys. Rev. Lett. 57, 2423–2426 (1986).

    Article  Google Scholar 

  26. 26.

    Murazawa, N. et al. Control of the molecular alignment inside liquid-crystal droplets by use of laser tweezers. Small 1, 656–661 (2005).

    Article  Google Scholar 

  27. 27.

    Choi, H. & Takezoe, H. Circular flow formation triggered by Marangoni convection in nematic liquid crystal films with a free surface. Soft Matter 12, 481–485 (2016).

    Article  Google Scholar 

  28. 28.

    Lehmann, O. Structur, system und magnetisches verhalten flüssiger krystalle und deren mischbarkeit mit festen. Ann. Phys. 307, 649–705 (1900).

    Article  Google Scholar 

  29. 29.

    Ignes-Mullol, J., Poy, G. & Oswald, P. Continuous rotation of achiral nematic liquid crystal droplets driven by heat flux. Phys. Rev. Lett. 117, 057801 (2016).

    Article  Google Scholar 

  30. 30.

    Tabe, Y. & Yokoyama, H. Coherent collective precession of molecular rotors with chiral propellers. Nat. Mater. 2, 806–809 (2003).

    Article  Google Scholar 

  31. 31.

    van Es, J. J. G. S., Biemans, H. A. M. & Meijer, E. W. Synthesis and characterization of optically active cyclic 6,6′-dinitro-1,1′-binaphthyl-2,2′-diethers. Tetrahedron 8, 1825–1831 (1997).

    Article  Google Scholar 

  32. 32.

    Gerber, P. R. On the determination of the cholesteric screw sense by the Grandjean–Cano-method. Z. Nat. 35, 619–622 (1980).

    Google Scholar 

  33. 33.

    Aßhoff, S. J. et al. Time-programmed helix inversion in phototunable liquid crystals. Chem. Commun. 49, 4256–4258 (2013).

    Article  Google Scholar 

Download references

Acknowledgements

This research was supported financially by the H2020-MSCA-IF-2014 programme (Grant 661315 to T.O.), the Netherlands Organization for Scientific Research (FOM Grant 13PR3105 to F.L. and N.K.), and the European Research Council (Starting Grant 307784 to N.K.).

Author information

Affiliations

Authors

Contributions

E.B. and N.K. initiated and guided the research. The laser experiments were designed by E.B. and performed by T.O. and C.L. The light-responsive liquid crystals were designed by N.K. and prepared by F.L. and S.I. S.I. synthesized the molecular motors. E.B. conceived the model. E.B. and T.O. performed the simulations. E.B., N.K., T.O. and F.L. analysed the data and discussed the results at all stages. E.B. and N.K. wrote the manuscript.

Corresponding authors

Correspondence to Nathalie Katsonis or Etienne Brasselet.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Captions for Supplementary Videos, Supplementary Figures 1–9; Supplementary Table 1; Supplementary Schemes 1–3.

Videos

Supplementary Video 1

Counter-clockwise rotation of a twisted topological structure with a diameter d ~ 45 µm.

Supplementary Video 2

Clockwise rotation of twisted topological structure with a diameter d ~ 45 µm.

Supplementary Video 3

Clockwise rotation of twisted topological structure with a diameter d ~ 50 µm.

Supplementary Video 4

Emergence of a twisted topological structure, when a cholesteric liquid crystal undergoes helix inversion under illumination.

Supplementary Video 5

Emergence of a twisted topological structure, when a cholesteric liquid crystal does not undergo helix inversion under illumination.

Supplementary Video 6

Orbital transport of a satellite cargo, along a clockwise trajectory.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Orlova, T., Lancia, F., Loussert, C. et al. Revolving supramolecular chiral structures powered by light in nanomotor-doped liquid crystals. Nature Nanotech 13, 304–308 (2018). https://doi.org/10.1038/s41565-017-0059-x

Download citation

Further reading

Search

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research