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Pumping between phases with a pulsed-fuel molecular ratchet

Nature Nanotechnology volume 17, pages 701–707 (2022)Cite this article

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Abstract

The sorption of species from a solution into and onto solids underpins the sequestering of waste and pollutants, precious metal recovery, heterogeneous catalysis, analysis and separation science, and other technologies1,2. The transfer between phases tends to proceed spontaneously in the direction of equilibrium. For example, alkyl ammonium groups mounted on silica nanoparticles are used to chemisorb cucurbituril macrocycles from solution through host–guest binding3,4. Molecular ratchet mechanisms5,6,7, in which kinetic gating8,9,10,11,12 inhibits or accelerates particular steps, makes it possible to progressively drive dynamic systems13,14,15,16 away from equilibrium17,18,19,20,21. Here we report on molecular pumps22 immobilized on polymer beads23,24,25 that use an energy ratchet mechanism5,9,19,20,21,26,27,28,29,30 to directionally transport substrates from solution onto the beads. On the addition of trichloroacetic acid (CCl3CO2H)19,31,32,33 fuel19,34,35,36,37, micrometre-diameter polystyrene beads functionalized38 with solvent-accessible molecular pumps sequester from the solution crown ethers appended with fluorescent tags. After fuel consumption, the rings are mechanically trapped in a higher-energy, out-of-equilibrium state on the beads and cannot be removed by dilution or exhaustive washing. This differs from dissipative assembled materials11,13,14,15,16, which require a continuous supply of energy to persist, and from conventional host–guest complexes. The addition of a second fuel pulse causes the uptake of more macrocycles, which drives the system further away from equilibrium. The second macrocycle can be labelled with a different fluorescent tag, which confers sequence information39 on the absorbed structure. The polymer-bound substrates can be released back to the bulk either one compartment at a time or all at once. Non-equilibrium40 sorption by immobilized artificial molecular machines41,42,43,44,45 enables the transduction of energy from chemical fuels for the use, storage and release of energy and information.

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Fig. 1: Pumping from solution to the solvent-accessible sites of polymer beads with a pulsed chemical fuel.
Fig. 2: Stepwise operation of molecular pump 1 in solution.
Fig. 3: Partial 1H NMR (600 MHz, CD3CN, 298 K) spectra for the operation of molecular ratchet 1 in solution.
Fig. 4: Sequential pumping from solution onto polymer beads with a pulsed chemical fuel.
Fig. 5: Reading sequence information stored in ratcheted rotaxane polymer beads.

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Data availability

The data that support the findings of this study are available within the article and its Supplementary Information.

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Acknowledgements

We thank S. Webb and D. Heyes for assistance with the fluorescence microscopy and spectroscopy, S. D. P. Fielden for useful discussions, the University of Manchester Mass Spectrometry Service Centre for high-resolution mass spectrometry, the Engineering and Physical Sciences Research Council (EPSRC; EP/P027067/1) and the EU (European Research Council (ERC); Advanced grant number 786630) for funding, the University of Manchester for a President’s Scholarship (to D.T.), Marie Skłodowska-Curie Actions of the European Union (individual postdoctoral fellowship 892035 to Y.R.) and J. F. Stoddart for the advanced disclosure of Feng et al.52. D.A.L. is a Royal Society Research Professor.

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Authors and Affiliations

  1. Department of Chemistry, University of Manchester, Manchester, UK

    Dean Thomas, Daniel J. Tetlow, Yansong Ren, Salma Kassem, Ulvi Karaca & David A. Leigh

  2. School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China

    David A. Leigh

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D.T., D.J.T., Y.R., S.K. and U.K. planned and carried out the experimental work 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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Correspondence to David A. Leigh.

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Supplementary Figs. 1–21, Schemes 1–10 and Spectra 1–75.

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Thomas, D., Tetlow, D.J., Ren, Y. et al. Pumping between phases with a pulsed-fuel molecular ratchet. Nat. Nanotechnol. 17, 701–707 (2022). https://doi.org/10.1038/s41565-022-01097-1

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