Dissipative self-assembly of vesicular nanoreactors

Abstract

Dissipative self-assembly is exploited by nature to control important biological functions, such as cell division, motility and signal transduction. The ability to construct synthetic supramolecular assemblies that require the continuous consumption of energy to remain in the functional state is an essential premise for the design of synthetic systems with lifelike properties. Here, we show a new strategy for the dissipative self-assembly of functional supramolecular structures with high structural complexity. It relies on the transient stabilization of vesicles through noncovalent interactions between the surfactants and adenosine triphosphate (ATP), which acts as the chemical fuel. It is shown that the lifetime of the vesicles can be regulated by controlling the hydrolysis rate of ATP. The vesicles sustain a chemical reaction but only as long as chemical fuel is present to keep the system in the out-of-equilibrium state. The lifetime of the vesicles determines the amount of reaction product produced by the system.

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Figure 1: Formation and characterization of vesicles.
Figure 2: Transient formation of vesicles.
Figure 3: Product formation as a function of vesicle lifetime.

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Acknowledgements

This work was financially supported by the European Commission (grant MSCA 657486 to S.M.), COST Action CM1304 (to L.J.P.), the University of Padova (grant CPDA138148 to L.J.P.) and the Italian Ministry of Education and Research (grant PRIN2010C4R8M8 to C.F.). Full data are provided in the Supplementary Information. ESEM measurements were performed by C. Furlan at the CE.A.S.C. at the University of Padova. CryoTEM measurements were performed by E. Paccagnini in the Electron Microscopy Laboratory of the Department of Life Sciences at the University of Siena (director, P. Lupetti). The authors thank J. Chen for a critical assessment of the manuscript, M. Zerbetto for discussions on the FCS analysis and M. Zangrossi for preparation of the movies.

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S.M. and L.J.P. designed the experiments. S.M. performed all experiments, except for the FCS and confocal microscopy studies, which were performed by I.F. L.J.P. wrote models T, K1 and K2 and performed fitting and simulations. C.F. and P.S. were involved in data interpretation. L.J.P. wrote the manuscript and all authors commented on it.

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Correspondence to Leonard J. Prins.

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The authors declare no competing financial interests.

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Maiti, S., Fortunati, I., Ferrante, C. et al. Dissipative self-assembly of vesicular nanoreactors. Nature Chem 8, 725–731 (2016). https://doi.org/10.1038/nchem.2511

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