Enhanced catalytic activity under non-equilibrium conditions

Abstract

The development of non-equilibrium synthetic systems provides access to innovative materials with life-like properties. Non-equilibrium systems require a continuous input of energy to retain their functional state, which makes for a fundamental difference to systems that operate at thermodynamic equilibrium. Kinetic asymmetry in the energy consumption pathway is required to drive systems out of equilibrium. This understanding has permitted chemists to design dissipative synthetic molecular machines and high-energy materials. Here we show that kinetic asymmetry also emerges at the macroscopic level by demonstrating that local energy delivery in the form of light to a hydrogel containing gold nanoparticles installs a non-equilibrium steady state. The instalment and maintenance of the macroscopic non-equilibrium state is facilitated by the gel matrix in which motion is governed by diffusion rather than convection. The non-equilibrium state is characterized by a persistent gradient in the surface composition of the nanoparticles embedded in the gel, which affects the fluorescent and catalytic properties of the system. We show that the overall catalytic performance of the system is enhanced under these non-equilibrium conditions. In perspective it will be possible to develop out-of-equilibrium matrices in which functional properties emerge as a result of spatially controlled energy delivery and spatially controlled chemistries.

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Fig. 1: Spatially controlled signal generation in a hydrogel.
Fig. 2: Simulations of light-induced diffusion in the hydrogel.
Fig. 3: Experimental and simulated catalytic activity on local irradiation.
Fig. 4: Enhanced catalysis under non-equilibrium conditions.

Data availability

The data that support the findings of this study are available from the corresponding author on reasonable request.

References

  1. 1.

    Branscomb, E., Biancalani, T., Goldenfeld, N. & Russell, M. Escapement mechanisms and the conversion of disequilibria; the engines of creation. Phys. Rep. 677, 1–60 (2017).

    Article  Google Scholar 

  2. 2.

    Gnesotto, F. S., Mura, F., Gladrow, J. & Broedersz, C. P. Broken detailed balance and non-equilibrium dynamics in living systems: a review. Rep. Prog. Phys. 81, 066601 (2018).

    CAS  Article  Google Scholar 

  3. 3.

    Astumian, R. D. Microscopic reversibility as the organizing principle of molecular machines. Nat. Nanotechnol. 7, 684–688 (2012).

    CAS  Article  Google Scholar 

  4. 4.

    Desai, A. & Mitchison, T. J. Microtubule polymerization dynamics. Annu. Rev. Cell Dev. Biol. 13, 83–117 (1997).

    CAS  Article  Google Scholar 

  5. 5.

    Feher, J. Quantitative Human Physiology (Academic Press, 2017).

  6. 6.

    Kicheva, A., Cohen, M. & Briscoe, J. Developmental pattern formation: insights from physics and biology. Science 338, 210–212 (2012).

    CAS  Article  Google Scholar 

  7. 7.

    Wang, W., Duan, W. T., Ahmed, S., Mallouk, T. E. & Sen, A. Small power: autonomous nano- and micromotors propelled by self-generated gradients. Nano Today 8, 531–554 (2013).

    CAS  Article  Google Scholar 

  8. 8.

    Mattia, E. & Otto, S. Supramolecular systems chemistry. Nat. Nanotechnol. 10, 111–119 (2015).

    CAS  Article  Google Scholar 

  9. 9.

    Grzybowski, B. A. & Huck, W. T. S. The nanotechnology of life-inspired systems. Nat. Nanotechnol. 11, 584–591 (2016).

    Article  Google Scholar 

  10. 10.

    Ashkenasy, G., Hermans, T. M., Otto, S. & Taylor, A. F. Systems chemistry. Chem. Soc. Rev. 46, 2543–2554 (2017).

    CAS  Article  Google Scholar 

  11. 11.

    Astumian, R. D. Design principles for brownian molecular machines: how to swim in molasses and walk in a hurricane. Phys. Chem. Chem. Phys. 9, 5067–5083 (2007).

    CAS  Article  Google Scholar 

  12. 12.

    Kassem, S. et al. Artificial molecular motors. Chem. Soc. Rev. 46, 2592–2621 (2017).

    CAS  Article  Google Scholar 

  13. 13.

    Prins, L. J. Emergence of complex chemistry on an organic monolayer. Acc. Chem. Res. 48, 1920–1928 (2015).

    CAS  Article  Google Scholar 

  14. 14.

    Manea, F., Houillon, F. B., Pasquato, L. & Scrimin, P. Nanozymes: gold-nanoparticle-based transphosphorylation catalysts. Angew. Chem. Int. Ed. 43, 6165–6169 (2004).

    CAS  Article  Google Scholar 

  15. 15.

    Pieters, G., Cazzolaro, A., Bonomi, R. & Prins, L. J. Self-assembly and selective exchange of oligoanions on the surface of monolayer protected Au nanoparticles in water. Chem. Commun. 48, 1916–1918 (2012).

    CAS  Article  Google Scholar 

  16. 16.

    Sapsford, K. E., Berti, L. & Medintz, I. L. Materials for fluorescence resonance energy transfer analysis: beyond traditional donor-acceptor combinations. Angew. Chem. Int. Ed. 45, 4562–4588 (2006).

    CAS  Article  Google Scholar 

  17. 17.

    Neri, S., Martin, S. G., Pezzato, C. & Prins, L. J. Photoswitchable catalysis by a nanozyme mediated by a light-sensitive cofactor. J. Am. Chem. Soc. 139, 1794–1797 (2017).

    CAS  Article  Google Scholar 

  18. 18.

    Wei, H. & Wang, E. K. Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes. Chem. Soc. Rev. 42, 6060–6093 (2013).

    CAS  Article  Google Scholar 

  19. 19.

    Pezzato, C., Scrimin, P. & Prins, L. J. Zn2+-regulated self-sorting and mixing of phosphates and carboxylates on the surface of functionalized gold nanoparticles. Angew. Chem. Int. Ed. 53, 2104–2109 (2014).

    CAS  Article  Google Scholar 

  20. 20.

    Le Saux, T., Plasson, R. & Jullien, L. Energy propagation throughout chemical networks. Chem. Commun. 50, 6189–6195 (2014).

    Article  Google Scholar 

  21. 21.

    Emond, M. et al. Energy propagation through a protometabolism leading to the local emergence of singular stationary concentration profiles. Chem. Eur. J. 18, 14375–14383 (2012).

    CAS  Article  Google Scholar 

  22. 22.

    Fersht, A. Structure and Mechanism in Protein Science. A Guide to Enzyme Catalysis and Protein Folding (W. H. Freeman and Company, 1999).

  23. 23.

    Pezzato, C. & Prins, L. J. Transient signal generation in a self-assembled nanosystem fueled by ATP. Nat. Commun. 6, 7790 (2015).

    CAS  Article  Google Scholar 

  24. 24.

    Astumian, R. D. Stochastic pumping of non-equilibrium steady-states: how molecules adapt to a fluctuating environment. Chem. Commun. 54, 427–444 (2018).

    CAS  Article  Google Scholar 

  25. 25.

    Ragazzon, G. & Prins, L. J. Energy consumption in chemical fuel-driven self-assembly. Nat. Nanotechnol. 13, 882–889 (2018).

    CAS  Article  Google Scholar 

  26. 26.

    Astumian, R. D. Kinetic asymmetry allows macromolecular catalysts to drive an information ratchet. Nat. Commun. 10, 3837 (2019).

    Article  Google Scholar 

  27. 27.

    Penocchio, E., Rao, R. & Esposito, M. Thermodynamic efficiency in dissipative chemistry. Nat. Commun. 10, 3865 (2019).

    Article  Google Scholar 

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Acknowledgements

The research was financially supported by the China Science Council (R.C.) and the Italian Ministry of Education and Research (L.J.P., grant no. 2017E44A9P). T. Carofiglio is acknowledged for preparation of the masks. J. Czescik is acknowledged for providing the substrate HPNPP. M. Troiani is acknowledged for contributing to the synthesis of compound A.

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R.C. and L.J.P. designed the experiments. R.C. carried out all experiments. S.N. performed preliminary experiments. L.J.P. wrote the kinetic models and performed the simulations. R.C. and L.J.P. wrote the manuscript.

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Correspondence to Leonard J. Prins.

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Supplementary Information

Supplementary Methods, Figs. 1–37, Tables 1–17, Scheme 1 and refs. 1–2.

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Chen, R., Neri, S. & Prins, L.J. Enhanced catalytic activity under non-equilibrium conditions. Nat. Nanotechnol. 15, 868–874 (2020). https://doi.org/10.1038/s41565-020-0734-1

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