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Coherent collective precession of molecular rotors with chiral propellers

Abstract

Successful attempts to manufacture synthetic molecular motors have recently been reported1,2. However, compared with natural systems such as motor proteins3,4,5,6, synthetic motors are smaller molecules and are therefore subject to thermal fluctuations that prevent them from performing any useful function7. A mechanism is needed to amplify the single molecular motion to such a level that it becomes distinguishable from the thermal background. Condensation of molecular motors into soft ordered phases (such as liquid crystals) will be a feasible approach, because there is evidence that they support molecularly driven non-equilibrium motions8,9,10. Here we show that a chiral liquid-crystalline monolayer spread on a glycerol surface acts as a condensed layer of molecular rotors, which undergo a coherent molecular precession driven by the transmembrane transfer of water molecules. Composed of simple rod-like molecules with chiral propellers, the monolayer exhibits a spatiotemporal pattern in molecular orientations that closely resembles 'target patterns' in Belousov–Zhabotinsky reactions11. Inversion of either the molecular chirality or the transfer direction of water molecules reverses the rotation direction associated with switching from expanding to converging target patterns. Endowed only with the soft directional order, the liquid crystal is an optimal medium that helps molecular motors to manifest their individual motions collectively.

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Figure 1: The chemical structure of (R)-OPOB and an exaggerated diagram of its Langmuir monolayer spread on glycerol.
Figure 2: Sequential micrographs of (R)-OPOB monolayer on pure glycerol and the corresponding simulation (top right) indicating the distribution of the tilt azimuth φ.
Figure 3: Temporal change of the reflected light intensity from the chiral monolayers on glycerol at room temperature, averaged over 300 ÎĽm2 of the central area of the target pattern.
Figure 4: Plot of molecular precession frequency against relative water vapour pressure for (R)-OPOB and (S)-OPOB monolayers on a glycerol–water mixture at different relative humidities.

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Acknowledgements

We thank J. Li, Clariant Japan and S. Naemura, Merck, Japan for generous provision of the LC compounds.

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41563_2003_BFnmat1017_MOESM1_ESM.mov

The real-time movie of the CW molecular rotation in (R)-OPOB monolayer on pure glycerol at 45% RH and room temperature. (MOV 982 kb)

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Tabe, Y., Yokoyama, H. Coherent collective precession of molecular rotors with chiral propellers. Nature Mater 2, 806–809 (2003). https://doi.org/10.1038/nmat1017

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