Photoswitchable gating of non-equilibrium enzymatic feedback in chemically communicating polymersome nanoreactors
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Author(s)
Type
Journal Article
Abstract
The circadian rhythm generates out-of-equilibrium metabolite oscillations controlled by feedback
loops under light/dark cycles. Here we describe a non-equilibrium nanosystem comprising a binary
population of enzyme-containing polymersomes capable of light-gated chemical communication,
controllable feedback and coupling to macroscopic oscillations. The populations consist of esterase-
containing polymersomes functionalised with photo-responsive Donor-Acceptor Stenhouse Adducts
(DASA) and light-insensitive semi-permeable urease-loaded polymersomes. The DASA-polymersome
membrane becomes permeable under green light, switching on esterase activity and decreasing the
pH, which in turn initiates production of alkali in the urease-containing population. A pH-sensitive
pigment that absorbs green light when protonated provides a negative feedback loop for deactivating
the DASA-polymersomes. Simultaneously, increased alkali production deprotonates the pigment, re-
activating esterase activity by opening the membrane gate. We utilise light-mediated fluctuations of
pH to perform non-equilibrium communication between the nanoreactors and use the feedback loops
to induce work as chemomechanical swelling/deswelling oscillations in a crosslinked hydrogel. We
envision possible applications in artificial organelles, protocells, and soft robotics.
loops under light/dark cycles. Here we describe a non-equilibrium nanosystem comprising a binary
population of enzyme-containing polymersomes capable of light-gated chemical communication,
controllable feedback and coupling to macroscopic oscillations. The populations consist of esterase-
containing polymersomes functionalised with photo-responsive Donor-Acceptor Stenhouse Adducts
(DASA) and light-insensitive semi-permeable urease-loaded polymersomes. The DASA-polymersome
membrane becomes permeable under green light, switching on esterase activity and decreasing the
pH, which in turn initiates production of alkali in the urease-containing population. A pH-sensitive
pigment that absorbs green light when protonated provides a negative feedback loop for deactivating
the DASA-polymersomes. Simultaneously, increased alkali production deprotonates the pigment, re-
activating esterase activity by opening the membrane gate. We utilise light-mediated fluctuations of
pH to perform non-equilibrium communication between the nanoreactors and use the feedback loops
to induce work as chemomechanical swelling/deswelling oscillations in a crosslinked hydrogel. We
envision possible applications in artificial organelles, protocells, and soft robotics.
Date Issued
2022-11-07
Date Acceptance
2022-09-14
Citation
Nature Chemistry, 2022, 15, pp.110-118
ISSN
1755-4330
Publisher
Nature Research
Start Page
110
End Page
118
Journal / Book Title
Nature Chemistry
Volume
15
Copyright Statement
© The Author(s) 2022. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
License URL
Identifier
https://doi.org/10.1038/s41557-022-01062-4
Publication Status
Published
Date Publish Online
2022-11-07