Reißenweber Lilli, Uhl Edgar, Hampel Frank, Mayer Peter, Dube Henry
Department of Chemistry and Pharmacy, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nikolaus-Fiebiger-Str. 10, 91058 Erlangen, Germany.
Department of Chemistry and Munich Center for Integrated Protein Science CIPSM, Ludwig-Maximilians-Universität München, D-81377 Munich, Germany.
J Am Chem Soc. 2024 Aug 21;146(33):23387-23397. doi: 10.1021/jacs.4c06377. Epub 2024 Aug 7.
Molecular motors are central driving units for nanomachinery, and control of their directional motions is of fundamental importance for their functions. Light-driven variants use easy to provide, easy to dose, and waste-free fuel with high energy content, making them particularly interesting for applications. Typically, light-driven molecular motors work via rotations around dedicated chemical bonds where the directionality of the rotation is dictated by the steric effects of asymmetry in close vicinity to the rotation axis. In this work, we show how unidirectional rotation around a virtual axis can be realized by reprogramming a molecular motor. To this end, a classical light-driven motor is restricted by macrocyclization, and its intrinsic directional rotation is transformed into a directional rotation of the macrocyclic chain in the opposite direction. Further, solvent polarity changes allow to toggle the function of this molecular machine between a directional motor and a nondirectional photoswitch. In this way, a new concept for the design of molecular motors is delivered together with elaborate control over their motions and functions by simple solvent changes. The possibility of sensing the environmental polarity and correspondingly adjusting the directionality of motions opens up a next level of control and responsiveness to light-driven nanoscopic motors.
分子马达是纳米机械的核心驱动单元，控制其定向运动对其功能至关重要。光驱动变体使用易于提供、易于计量且无浪费的高能量燃料，这使其在应用中特别受关注。通常，光驱动分子马达通过围绕特定化学键的旋转来工作，其中旋转的方向性由靠近旋转轴的不对称空间效应决定。在这项工作中，我们展示了如何通过对分子马达进行重新编程来实现围绕虚拟轴的单向旋转。为此，一个经典的光驱动马达通过大环化受到限制，其固有的定向旋转被转化为大环链在相反方向的定向旋转。此外，溶剂极性的变化允许在定向马达和非定向光开关之间切换这种分子机器的功能。通过这种方式，提出了一种分子马达设计的新概念，同时通过简单的溶剂变化对其运动和功能进行精细控制。感知环境极性并相应调整运动方向性的可能性为光驱动纳米马达开启了更高层次的控制和响应能力。
