Building an Autonomous Chemically-Fuelled Rotary Molecular Motor

以化学为燃料的分子马达在自然界中无处不在，它自动将能量转化为功或运动，为生物过程提供动力。合成分子马达作为未来纳米级技术的组成部分具有潜力1，然而要实现分子运动的自主性仍然是一个具有挑战性的方面。到目前为止，只有一种基于顺丁烯二环结构的人造化学燃料发动机被报道过。2在这个项目中，我们的目标是开发能够围绕单键进行单向化学燃料自主旋转运动的联芳基发动机。开发自主马达的关键将是探索循环化学反应网络(CRN)，即在其中相反的、非微观上可逆的反应同时发生的系统，导致两个或两个以上状态之间底物的重复化学转化3。人们希望，除了创造一个能够自主运动的系统外，拟议中的马达的合成简单性将使这些分子机器的开发应用在未来更容易获得。该项目将使用合成有机化学来获得发展这些化学反应网络所需的底物，以及各种分析技术，如核磁共振标记和动力学研究，以分析系统的动态非平衡行为，并证明连续的旋转运动。埃尔巴斯-卡马克，S.；利，D.A.；麦克特南，C.T.；努斯鲍默，A.L.，人工分子机器。化学。2015年版，第115(18)页，10081-10206页。威尔逊，M.R.；索拉，J.；卡隆，A.；Goldup，S.M.；LeBrasseur，N.；Leigh，D.A.，自然，2016,534(7606)，235-240。Riess B.；Grötsch，R.K.；Boekhoven，J.，Chem 2020，6(3)，552-578。

Chemically fuelled molecular motors are ubiquitous in nature, autonomously converting energy into work or motion to power biological processes. Synthetic molecular motors hold potential as components in future nanoscale technologies,1 however autonomy remains a challenging aspect of molecular motion to achieve. To date, only one artificial chemically-fuelled motor with this feature has been reported, based on a catenane architecture.2 In this project, we aim to develop biaryl motors capable of unidirectional chemically-fuelled autonomous rotary motion around a single bond. Key to developing an autonomous motor will be the exploration of cyclical chemical reaction networks (CRNs), that is, systems in which opposing, non-microscopically reversible reactions occur concurrently, resulting in the repeated chemical transformation of substrates between two or more states3. It is hoped that, in addition to creating a system capable of autonomous motion, the synthetic simplicity of the proposed motors will make developing applications for these molecular machines more accessible in future. This project will employ synthetic organic chemistry to access the substrates necessary for the development of these chemical reaction networks, as well as a variety of analytical techniques such as NMR labelling and kinetics studies to analyse the dynamic non-equilibrium behaviour of the system and prove continuous rotary motion. Erbas-Cakmak, S.; Leigh, D. A.; McTernan, C. T.; Nussbaumer, A. L., Artificial Molecular Machines. Chem. Rev. 2015, 115 (18), 10081-10206. Wilson, M. R.; Solà, J.; Carlone, A.; Goldup, S. M.; Lebrasseur, N.; Leigh, D. A., Nature 2016, 534 (7606), 235-240. Riess, B.; Grötsch, R. K.; Boekhoven, J., Chem 2020, 6 (3), 552-578.