[1,n]-Metal migrations for directional translational motion at the molecular level

Beatrice, Collins, Emma, Hollis, Michael, Chronias, Carlijn, van Beek, Paul, Gates
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Abstract

The controlled translational motion displayed by nature’s motor proteins underpins a wealth of processes integral to life, from organelle transport to muscle contraction. The motor proteins move along one dimensional cytoskeletal tracks, with their motion characterised by high association of the enzyme to the biopolymer combined with highly dynamic motion along the track. Efforts to mimic this dynamic association and control translational motion in fully synthetic systems have been dominated by rotaxane-based systems, where the properties of the mechanical bond ensure complete association between the moving component (the macrocycle) and the track it encircles, while allowing high rates of translation through shuttling of the moving component under Brownian motion. In addition to the dynamic association displayed by many rotaxane systems, by careful design of the track and macrocyclic component, elegant strategies have been employed to further control the motion in these mechanically interlocked systems, with both energy and information ratchet mechanisms allowing directional translational motion to be achieved. Other than mechanical bonds, alternative platforms for achieving controlled translational motion in fully synthetic systems have had more limited success, with bipedal walker systems that exhibit dynamic association lacking mechanisms to achieve inherent directionality, and bipedal systems that do display high levels of directionality requiring stepwise intervention of an experimentalist (i.e., they lack the dynamic autonomous behaviour that underpins nature’s walkers). Here we introduce carbon-to-carbon metal migration as a new platform for dynamic association and show how such migrations, in combination with the incorporation of a simple hydrocarbon fuel, can be harnessed to achieve autonomous directional translational motion of a metal centre along the length of a polyaromatic thread.
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分子水平上定向平移运动的[1,n]-金属迁移
从细胞器运输到肌肉收缩,大自然中的运动蛋白所表现出的受控平移运动支撑着生命中不可或缺的大量过程。运动蛋白沿着一维细胞骨架轨道运动,其运动特点是酶与生物聚合物的高度结合以及沿着轨道的高度动态运动。在全合成系统中模拟这种动态关联和控制平移运动的努力主要是以轮烷为基础的系统,在这种系统中,机械键的特性确保了运动部件(大循环)和它所环绕的轨道之间的完全关联,同时通过运动部件在布朗运动下的穿梭,允许高速平移。除了许多轮烷系统显示出的动态结合之外,通过对轨道和大环成分进行精心设计,还采用了优雅的策略来进一步控制这些机械互锁系统中的运动,能量和信息棘轮机制可实现定向平移运动。除了机械键之外,在全合成系统中实现可控平移运动的其他平台取得的成功比较有限,表现出动态关联的双足步行者系统缺乏实现固有方向性的机制,而表现出高度方向性的双足系统则需要实验人员的逐步干预(即它们缺乏自然界步行者的动态自主行为)。在这里,我们引入了碳到碳的金属迁移作为动态关联的新平台,并展示了如何利用这种迁移,结合简单的碳氢化合物燃料,实现金属中心沿着多芳香族线的长度自主定向平移运动。
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