Electrostatic Forces in Field-Perturbed Equilibria: Nanopore Analysis of Cage Complexes
Electrostatic Forces in Field-Perturbed Equilibria: Nanopore Analysis of Cage Complexes
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DOI：
10.1016/j.chempr.2019.03.004
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发表时间：
2019-05-09
期刊：
影响因子：
23.5
通讯作者：
Cockroft, Scott L.
中科院分区：
文献类型：
--
作者：
Borsley, Stefan;Haugland, Marius M.;Cockroft, Scott L.
平衡条件下的分子识别已被广泛研究，但很少有人知道这样的过程时，受到外力的干扰。在这里，我们研究了电场对金属超分子笼和蛋白质纳米孔在单分子水平上形成的复合物的影响。缔合速率主要由所施加的电压，而笼和纳米孔之间的局部静电相互作用更大地影响解离动力学。通过利用这些原理，我们表明，外部施加的电压可以用来选择性地结合一个特定的笼从一个混合物含有大量过剩的其他笼。此外，所施加的电压也可以用于驱动手性笼的超分子对映体转化，或者偶尔驱动纳米孔深处笼的非平衡捕获和分解。类似的原理可以用于设计在外部施加的电场或生物跨膜电位内操作的其他分子装置。
Molecular recognition has been widely investigated under equilibrium conditions, but little is known about such processes when perturbed by external forces. Here, we investigate the influence of electric fields on complexes formed between metallosupramolecular cages and a protein nanopore at the single-molecule level. Association rates were dominated by the applied voltage, whereas local electrostatic interactions between the cage and the nanopore more greatly influenced the dissociation kinetics. By exploiting these principles, we showed that the externally applied voltage could be used to selectively bind a specific cage from a mixture containing a large excess of other cages. Moreover, the applied voltage could also be used to drive supramolecular enantioinversion of the chiral cages or, occasionally, the non-equilibrium capture and disassembly of cages deep within the nanopore. Similar principles might be exploited in the design of other molecular devices that operate within externally applied electric fields or biogenic transmembrane potentials.