Fu Heyifei, Pramanik Susnata, Aprahamian Ivan
6128 Burke Laboratory, Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, United States.
Department of Chemistry, SRM Institute of Science and Technology, Kattankulathur 603203, India.
J Am Chem Soc. 2023 Sep 13;145(36):19554-19560. doi: 10.1021/jacs.3c02855. Epub 2023 Aug 29.
Transition metals play an important role in many biological processes including cellular regulation and signal transduction. Emulating such processes on the molecular level, while challenging, can help us learn how to manipulate intermolecular communication, an important requirement for the development of solution-based molecular machines. In this work, we demonstrate a transition metal-based artificial multistep switching cascade that exhibits intrinsic hierarchical level control. The process starts with Zn(II), which initiates a transition metal relay by displacing a macrocycle-encapsulated Pd(II). The latter then binds to a hydrazone switch leading to coordination-coupled deprotonation (CCD). Finally, the proton generated through CCD activates the / isomerization of a second noncoordinating pH-sensitive hydrazone switch. This whole multistep process can be reset to the original state by removing the Pd(II) from the system.
过渡金属在许多生物过程中发挥着重要作用,包括细胞调节和信号转导。在分子水平上模拟这些过程虽然具有挑战性,但可以帮助我们了解如何操纵分子间通信,这是基于溶液的分子机器发展的一项重要要求。在这项工作中,我们展示了一种基于过渡金属的人工多步开关级联反应,该反应具有内在的层次控制水平。该过程从Zn(II)开始,它通过取代大环封装的Pd(II)引发过渡金属中继。后者随后与腙开关结合,导致配位耦合去质子化(CCD)。最后,通过CCD产生的质子激活第二个非配位pH敏感腙开关的/异构化。通过从系统中去除Pd(II),整个多步过程可以重置为原始状态。