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An autonomous chemically fuelled small-molecule motor

Nature volume 534, pages 235–240 (2016)Cite this article

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Abstract

Molecular machines are among the most complex of all functional molecules and lie at the heart of nearly every biological process1. A number of synthetic small-molecule machines have been developed2, including molecular muscles3,4, synthesizers5,6, pumps7,8,9, walkers10, transporters11 and light-driven12,13,14,15,16 and electrically17,18 driven rotary motors. However, although biological molecular motors are powered by chemical gradients or the hydrolysis of adenosine triphosphate (ATP)1, so far there are no synthetic small-molecule motors that can operate autonomously using chemical energy (that is, the components move with net directionality as long as a chemical fuel is present)19. Here we describe a system in which a small molecular ring (macrocycle) is continuously transported directionally around a cyclic molecular track when powered by irreversible reactions of a chemical fuel, 9-fluorenylmethoxycarbonyl chloride. Key to the design is that the rate of reaction of this fuel with reactive sites on the cyclic track is faster when the macrocycle is far from the reactive site than when it is near to it. We find that a bulky pyridine-based catalyst promotes carbonate-forming reactions that ratchet the displacement of the macrocycle away from the reactive sites on the track. Under reaction conditions where both attachment and cleavage of the 9-fluorenylmethoxycarbonyl groups occur through different processes, and the cleavage reaction occurs at a rate independent of macrocycle location, net directional rotation of the molecular motor continues for as long as unreacted fuel remains. We anticipate that autonomous chemically fuelled molecular motors will find application as engines in molecular nanotechnology2,19,20.

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Figure 1: Operation of a chemically fuelled [2]catenane rotary motor.
Figure 2: [2]Rotaxane model system to demonstrate directional bias for Fmoc addition and position-independent Fmoc cleavage.
Figure 3: Exchange of Fmoc groups during stepwise operation of catenane 1.
Figure 4: Directional transport of the macrocycle monitored by 1H NMR spectroscopy.

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Acknowledgements

We thank D. R. Astumian for the analysis of the catenane motor reaction kinetics, the European Research Council (ERC) for funding and the EPSRC National Mass Spectrometry Service Centre (Swansea, UK) for high-resolution mass spectrometry.

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Author notes

  1. Jordi Solà, Armando Carlone, Stephen M. Goldup & Nathalie Lebrasseur

    Present address: †Present addresses: Institute of Advanced Chemistry of Catalonia (IQAC-CSIC), Jordi Girona 18-26, 08034 Barcelona, Spain (J.S.); Chirotech Technology Centre, Dr Reddy’s, Cambridge, CB4 0PE, UK (A.C.); Department of Chemistry, University of Southampton, Southampton SO17 1BJ, UK (S.M.G.); School of Biological and Chemical Sciences, Queen Mary University of London, London E1 4NS, UK (N.L.).,

  2. Jordi Solà and Armando Carlone: These authors contributed equally to this work.

Authors and Affiliations

  1. School of Chemistry, University of Manchester, Oxford Road, M13 9PL, Manchester, UK

    Miriam R. Wilson, Jordi Solà, Armando Carlone, Stephen M. Goldup, Nathalie Lebrasseur & David A. Leigh

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  1. Miriam R. Wilson
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Contributions

M.R.W., A.C., J.S., S.M.G. and N.L. carried out the experimental work. M.R.W. and J.S. designed and performed the operation experiments. D.A.L. directed the research. All the authors contributed to the analysis of the results and the writing of the manuscript.

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Correspondence to David A. Leigh.

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The authors declare no competing financial interests.

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This file contains Supplementary Text and Data, Supplementary Figures 1-77 and additional references (see Contents for more details). (PDF 10992 kb)

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Wilson, M., Solà, J., Carlone, A. et al. An autonomous chemically fuelled small-molecule motor. Nature 534, 235–240 (2016). https://doi.org/10.1038/nature18013

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