Abstract
Transport at the molecular scale is a prerequisite for the development of future molecular factories. Here, we have designed oligoanionic molecular sliders on polycationic tracks that exploit Brownian motion and diffusive binding to transport cargo without using a chemical fuel. The presence of the polymer tracks increases the rate of bimolecular reactions between modified sliders by over two orders of magnitude. Molecular dynamics simulations showed that the sliders not only diffuse, but also jump and hop surprisingly efficiently along polymer tracks. Inspired by acetyl-coenzyme A transporting and delivering acetyl groups in many essential biochemical processes, we developed a new and unconventional type of catalytic transport involving sliders (including coenzyme A) picking up, transporting and selectively delivering molecular cargo. Furthermore, we show that the concept of diffusive binding can also be utilized for the spatially controlled transport of chemical groups across gels. This work represents a new concept for designing functional nanosystems based on random Brownian motion.
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Data availability
The authors declare that all the data generated and analysed during this study are included within this Article and its Supplementary Information. The software and codes used to perform simulation and analysis are cited in the Article. The data sets are available from authors Y.H. and P.K. on reasonable request.
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Acknowledgements
This work was supported by the Netherlands Organization for Scientific Research (NWO) TOPPUNT grant 718.014.001 (to W.T.S.H.), the Ministry of Education, Culture and Science (Gravity programme, 024.001.035, to W.T.S.H.), an NSF DMR-1506886 grant (to P.K.) and by start-up funding from the University of Texas at El Paso (to L.V.). H.Z. is a recipient of a Radboud Excellence Fellowship.
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W.T.S.H. supervised the research. L.Z., H.Z. and W.T.S.H. planned the project and designed experiments. L.Z. and H.Z. synthesized and characterized all compounds. L.Z. and H.Z. performed kinetic studies of fluorogenic reactions and analysed data. L.Z. and H.Q. performed catalytic molecular transfer experiments and analysed data. L.Z. and J.M. analysed the ITC data. Y.H., L.V. and P.K. performed computational simulations. L.Z., Y.H., P.K. and W.T.S.H. wrote the manuscript.
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Experimental procedures, characterization of all compounds, and details of molecular dynamic simulations.
Supplementary Movie 1
Supplementary movie showing diffusion of Arg18-S-coumarin inside nc-PAAm gel matrix.
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Zheng, L., Zhao, H., Han, Y. et al. Catalytic transport of molecular cargo using diffusive binding along a polymer track. Nat. Chem. 11, 359–366 (2019). https://doi.org/10.1038/s41557-018-0204-7
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DOI: https://doi.org/10.1038/s41557-018-0204-7
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