Stratingh Institute for Chemistry, Center for Systems Chemistry and Zernike Institute for Advanced Materials, Faculty of Mathematics and Natural Sciences, University of Groningen, Groningen, the Netherlands.
Institut für Chemie und Biochemie der Freien Universität Berlin, Berlin, Germany.
Nat Nanotechnol. 2022 Feb;17(2):159-165. doi: 10.1038/s41565-021-01021-z. Epub 2021 Dec 16.
Biological molecular machines enable chemical transformations, assembly, replication and motility, but most distinctively drive chemical systems out of-equilibrium to sustain life. In such processes, nanometre-sized machines produce molecular energy carriers by driving endergonic equilibrium reactions. However, transforming the work performed by artificial nanomachines into chemical energy remains highly challenging. Here, we report a light-fuelled small-molecule ratchet capable of driving a coupled chemical equilibrium energetically uphill. By bridging two imine macrocycles with a molecular motor, the machine forms crossings and consequently adopts several distinct topologies by either a thermal (temporary bond-dissociation) or photochemical (unidirectional rotation) pathway. While the former will relax the machine towards the global energetic minimum, the latter increases the number of crossings in the system above the equilibrium value. Our approach provides a blueprint for coupling continuous mechanical motion performed by a molecular machine with a chemical transformation to reach an out-of-equilibrium state.
生物分子机器使化学转化、组装、复制和运动成为可能，但最显著的是将化学系统驱动出平衡状态以维持生命。在这些过程中，纳米机器通过驱动吸能平衡反应来产生分子能量载体。然而，将人工纳米机器所做的功转化为化学能仍然极具挑战性。在这里，我们报告了一种光驱动的小分子棘轮，它能够在能量上驱动耦合的化学平衡。通过用分子马达桥接两个亚胺大环，机器形成交叉点，并通过热（临时键断裂）或光化学（单向旋转）途径采用几种不同的拓扑结构。虽然前者将使机器向全局能量最低点松弛，但后者将系统中的交叉点数量增加到平衡值以上。我们的方法为将分子机器连续的机械运动与化学转化相结合以达到非平衡状态提供了蓝图。
