Autonomous fuelled directional rotation about a covalent single bond
Autonomous fuelled directional rotation about a covalent single bond
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DOI：
10.1038/s41586-022-04450-5
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发表时间：
2022-04-07
期刊：
影响因子：
64.8
通讯作者：
Roberts, Benjamin M. W.
中科院分区：
文献类型：
--
作者：
Borsley, Stefan;Kreidt, Elisabeth;Roberts, Benjamin M. W.
生物学通过自主的化学燃料分子机器（1）运行，包括旋转马达，如三磷酸腺苷合酶（2）和细菌鞭毛马达（3）。化学家长期以来一直试图创造类似的分子结构与化学动力，定向旋转，组件（4-17）。然而，能够围绕单键自主360度定向旋转的合成马达分子已被证明是难以捉摸的，先前的设计缺乏自主燃料（7，10，12）或方向性（6）。在这里，我们表明，1-苯基吡咯2，2 '-二羧酸（18，19）（1a）是一个催化驱动的（20，21）马达，可以连续地从化学燃料（9，20 -27）中吸收能量，以诱导两个芳环围绕连接它们的共价N-C键重复360度定向旋转。在用碳二亚胺处理1a时（21，25 -27），环之间的分子内酸酐形成和酸酐的水解都不断发生。两种反应都是动力学门控的（28-30），导致方向性偏差。因此，马达分子对碳二亚胺水合的催化连续驱动围绕N-C键的净定向旋转。方向性由加速酸酐水解的添加剂和燃料的手性决定，并且是容易反转的添加剂（31）。超过97%的燃料分子通过化学发动机循环（24）被消耗，具有高达71：29的方向偏差，具有手性匹配的燃料和添加剂。换句话说，电动机每转三到四圈就会出现一次方向上的“错误”。26个原子的马达分子的简单性预示着其结构优化和衍生物的开发，这些衍生物可以与其他组件连接以执行工作和任务（32-36）。
Biology operates through autonomous chemically fuelled molecular machinery(1), including rotary motors such as adenosine triphosphate synthase(2) and the bacterial flagellar motor(3). Chemists have long sought to create analogous molecular structures with chemically powered, directionally rotating, components(4-17). However, synthetic motor molecules capable of autonomous 360 degrees directional rotation about a single bond have proved elusive, with previous designs lacking either autonomous fuelling(7,10,12) or directionality(6). Here we show that 1-phenylpyrrole 2,2'-dicarboxylic acid(18,19) (1a) is a catalysis-driven(20,21) motor that can continuously transduce energy from a chemical fuel(9,20-27) to induce repetitive 360 degrees directional rotation of the two aromatic rings around the covalent N-C bond that connects them. On treatment of 1a with a carbodiimide(21,25-27), intramolecular anhydride formation between the rings and the anhydride's hydrolysis both occur incessantly. Both reactions are kinetically gated(28-30) causing directional bias. Accordingly, catalysis of carbodiimide hydration by the motor molecule continuously drives net directional rotation around the N-C bond. The directionality is determined by the handedness of both an additive that accelerates anhydride hydrolysis and that of the fuel, and is easily reversed additive(31). More than 97% of fuel molecules are consumed through the chemical engine cycle(24) with a directional bias of up to 71:29 with a chirality-matched fuel and additive. In other words, the motor makes a 'mistake' in direction every three to four turns. The 26-atom motor molecule's simplicity augurs well for its structural optimization and the development of derivatives that can be interfaced with other components for the performance of work and tasks(32-36).