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自主光驱动超分子泵耗散非平衡运行的动力学和能量学见解。

Kinetic and energetic insights into the dissipative non-equilibrium operation of an autonomous light-powered supramolecular pump.

机构信息

CLAN-Center for Light Activated Nanostructures, Istituto ISOF-CNR, Bologna, Italy.

Dipartimento di Chimica Industriale 'Toso Montanari', Università di Bologna, Bologna, Italy.

出版信息

Nat Nanotechnol. 2022 Jul;17(7):746-751. doi: 10.1038/s41565-022-01151-y. Epub 2022 Jun 27.

Abstract

Natural and artificial autonomous molecular machines operate by constantly dissipating energy coming from an external source to maintain a non-equilibrium state. Quantitative thermodynamic characterization of these dissipative states is highly challenging as they exist only as long as energy is provided. Here we report on the detailed physicochemical characterization of the dissipative operation of a supramolecular pump. The pump transduces light energy into chemical energy by bringing self-assembly reactions to non-equilibrium steady states. The composition of the system under light irradiation was followed in real time by H NMR for four different irradiation intensities. The experimental composition and photon flow were then fed into a theoretical model describing the non-equilibrium dissipation and the energy storage at the steady state. We quantitatively probed the relationship between the light energy input and the deviation of the dissipative state from thermodynamic equilibrium in this artificial system. Our results provide a testing ground for newly developed theoretical models for photoactivated artificial molecular machines operating away from thermodynamic equilibrium.

摘要

自然和人工自主分子机器通过不断耗散来自外部源的能量来维持非平衡态。这些耗散态的定量热力学特征具有很大的挑战性,因为它们只有在提供能量的情况下才会存在。在这里,我们报告了超分子泵耗散操作的详细物理化学特征。该泵通过将自组装反应推向非平衡稳态,将光能转化为化学能。在四种不同的辐照强度下,通过 H NMR 实时跟踪光照下系统的组成。然后,实验组成和光子流被输入到一个描述非平衡耗散和稳态储能的理论模型中。我们定量地探测了在这个人工系统中,光输入能量与耗散状态偏离热力学平衡之间的关系。我们的结果为新开发的远离热力学平衡运行的光激活人工分子机器的理论模型提供了一个测试平台。

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