Abstract
All biological pumps are autonomous catalysts; they maintain the out-of-equilibrium conditions of the cell by harnessing the energy released from their catalytic decomposition of a chemical fuel1,2,3. A number of artificial molecular pumps have been reported to date4, but they are all either fuelled by light5,6,7,8,9,10 or require repetitive sequential additions of reagents or varying of an electric potential during each cycle to operate11,12,13,14,15,16. Here we describe an autonomous chemically fuelled information ratchet17,18,19,20 that in the presence of fuel continuously pumps crown ether macrocycles from bulk solution onto a molecular axle without the need for further intervention. The mechanism uses the position of a crown ether on an axle both to promote barrier attachment behind it upon threading and to suppress subsequent barrier removal until the ring has migrated to a catchment region. Tuning the dynamics of both processes20,21 enables the molecular machine22,23,24,25 to pump macrocycles continuously from their lowest energy state in bulk solution to a higher energy state on the axle. The ratchet action is experimentally demonstrated by the progressive pumping of up to three macrocycles onto the axle from bulk solution under conditions where barrier formation and removal occur continuously. The out-of-equilibrium [n]rotaxanes (characterized with n up to 4) are maintained for as long as unreacted fuel is present, after which the rings slowly de-thread. The use of catalysis to drive artificial molecular pumps opens up new opportunities, insights and research directions at the interface of catalysis and molecular machinery.
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Data availability
The data that support the findings of this study are available within the paper and its Supplementary Information, or are available from the Mendeley data repository (https://data.mendeley.com/) at https://doi.org/10.17632/r339vx45sz.1.
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Acknowledgements
We thank the Engineering and Physical Sciences Research Council (EPSRC; grant number EP/P027067/1) and the European Research Council (ERC; Advanced Grant number 786630) for funding. We also thank the University of Manchester’s Department of Chemistry Services for mass spectrometry. D.A.L. is a Royal Society Research Professor.
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S.A. and S.D.P.F. carried out the synthesis and characterization studies. D.A.L. directed the research. All authors contributed to the analysis of the results and the writing of the manuscript.
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This Supplementary Information file contains the following sections: Abbreviations; General Information. Experimental Data; NMR Spectra; Supplementary Text (Optimisation of pumping conditions); and Supplementary References.
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Amano, S., Fielden, S.D.P. & Leigh, D.A. A catalysis-driven artificial molecular pump. Nature 594, 529–534 (2021). https://doi.org/10.1038/s41586-021-03575-3
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DOI: https://doi.org/10.1038/s41586-021-03575-3
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