A key goal of chemistry is to develop synthetic systems that mimic biology, such as self-assembling, self-replicating models of minimal life forms. Oscillations are often observed in complex biological networks, but oscillating, self-replicating species are unknown, and how to control autonomous supramolecular-level oscillating systems is also not yet established. Here we show how a population of self-assembling self-replicators can autonomously oscillate, so that simple micellar species repeatedly appear and disappear in time. The interplay of molecular and supramolecular events is key to observing oscillations: the repeated formation and disappearance of compartments is connected to a reaction network where molecular-level species are formed and broken down. The dynamic behaviour of our system across different length scales offers the opportunities for mass transport, as we demonstrate via reversible dye uptake. We believe these findings will inspire new biomimetic systems and may unlock nanotechnology systems such as (supra)molecular pumps, where compartment formation is controlled in time and space.
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The authors wish to thank E. Foley for help with iSCAT measurements and L. Carrique for performing cryo-transmission electron microscopy measurements. The authors thank the ERC (Consolidator Grant, Autocat, 681491) for funding. M.G.H. thanks the EPSRC Centre for Doctoral Training in Synthesis for Biology and Medicine (EP/L015838/1) for a studentship, generously supported by AstraZeneca, Diamond Light Source, Defence Science and Technology Laboratory, Evotec, GlaxoSmithKline, Janssen, Novartis, Pfizer, Syngenta, Takeda, UCB and Vertex. This work used the OPIC electron microscopy facility which is supported by a Wellcome JIF award (060208/Z/00/Z) and a Wellcome equipment grant (093305/Z/10/Z).
The authors declare no competing interests.
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Supplementary methods and synthesis, discussion and additional data.
Video of the visual oscillations seen when incorporating a hydrophobic dye (250× speed). Reaction is sampled for UPLC analysis.
Video of the visual oscillations seen when incorporating a hydrophobic dye (duplicate reaction, 250× speed). Reaction is not sampled or disturbed.
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Howlett, M.G., Engwerda, A.H.J., Scanes, R.J.H. et al. An autonomously oscillating supramolecular self-replicator. Nat. Chem. (2022). https://doi.org/10.1038/s41557-022-00949-6