英国帝国理工大学Stevens Molly M.团队报道了化学通讯聚合体纳米反应器中非平衡酶反馈的可光开关门控。相关研究成果发表在2022年11月7日出版的国际学术期刊《自然—化学》。

昼夜节律产生失衡的代谢物振荡，在光/暗循环下由反馈回路控制。

该文中，研究人员描述了一种非平衡纳米系统，该系统包括能够进行光门控化学通信、可控反馈和耦合到宏观振荡的含酶聚合体的二元群体。这些群体由含酯酶的聚合体和光敏半透性脲酶负载的聚合体组成，这些聚合体用光响应供体-受体-斯坦豪斯加合物（DASA）功能化。DASA–聚合酶体膜在绿光下变得可渗透，打开酯酶活性并降低pH值，进而启动含脲酶群体中碱的产生。

当质子化时，一种吸收绿光的pH敏感色素提供了一个负反馈回路，用于使DASA多聚体失活。同时，碱产量的增加使色素脱质子化，通过打开膜门重新激活酯酶活性。研究人员利用光介导的pH波动来执行纳米反应器之间的非平衡通信，并使用反馈回路来诱导交联水凝胶中的化学机械溶胀/去溶胀振荡。研究认为该成果可能在人工细胞器、原细胞和软机器人中应用。

附：英文原文

Title: Photoswitchable gating of non-equilibrium enzymatic feedback in chemically communicating polymersome nanoreactors

Author: Rifaie-Graham, Omar, Yeow, Jonathan, Najer, Adrian, Wang, Richard, Sun, Rujie, Zhou, Kun, Dell, Tristan N., Adrianus, Christopher, Thanapongpibul, Chalaisorn, Chami, Mohamed, Mann, Stephen, de Alaniz, Javier Read, Stevens, Molly M.

Issue&Volume: 2022-11-07

Abstract: The circadian rhythm generates out-of-equilibrium metabolite oscillations that are 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 functionalized with photo-responsive donor–acceptor Stenhouse adducts (DASA) and light-insensitive semipermeable urease-loaded polymersomes. The DASA–polymersome membrane becomes permeable under green light, switching on esterase activity and decreasing the pH, which in turn initiates the 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, reactivating esterase activity by opening the membrane gate. We utilize 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.

DOI: 10.1038/s41557-022-01062-4

Source: https://www.nature.com/articles/s41557-022-01062-4