中国科学院福建物构所尤磊团队报道了用于共价键和组合的变构和双向控制的光开关级联。相关研究成果发表在2024年4月15日出版的《美国化学会杂志》。

对复杂系统和模拟生物系统的新兴特性的研究处于化学研究的前沿。动态多步级联，尤其是那些表现出变构调节的级联，具有挑战性。

该文中，研究人员展示了一个多功能的光开关共价级联平台，用于远程和双向控制可逆共价键和随后的组装。光致变色开关、酮-烯醇平衡和环链平衡的中继能够使光介导的可逆变构结构变化。伴随而来的独特反应性进一步使底物能够通过交替的两种波长的光双向，进行光开关动态共价键合和释放，基本上实现了光介导的信号循环。

光化学反应中共价键形成/断裂导致的能量下降为级联的受控方向提供了驱动力。为了显示分子多样性，研究实现了共价聚合物（包括结构可重构的聚合物）的光开关按需组装/拆卸。

该项工作实现了动态多步级联中共价结构的光开关变构调节，这在以前很少报道。这些结果类似于生物信号网络中的变构控制为许多研究奠定基础，如动态组装、分子马达、响应聚合物和智能材料。

附：英文原文

Title: Photoswitchable Cascades for Allosteric and Bidirectional Control over Covalent Bonds and Assemblies

Author: Hanwei Lu, Hebo Ye, Lei You

Issue&Volume: April 15, 2024

Abstract: Studies of complex systems and emerging properties to mimic biosystems are at the forefront of chemical research. Dynamic multistep cascades, especially those exhibiting allosteric regulation, are challenging. Herein, we demonstrate a versatile platform of photoswitchable covalent cascades toward remote and bidirectional control of reversible covalent bonds and ensuing assemblies. The relay of a photochromic switch, keto–enol equilibrium, and ring–chain equilibrium allows light-mediated reversible allosteric structural changes. The accompanying distinct reactivity further enables photoswitchable dynamic covalent bonding and release of substrates bidirectionally through alternating two wavelengths of light, essentially realizing light-mediated signaling cycles. The downfall of energy by covalent bond formation/scission upon photochemical reactions offers the driving force for the controlled direction of the cascade. To show the molecular diversity, photoswitchable on-demand assembly/disassembly of covalent polymers, including structurally reconfigurable polymers, was realized. This work achieves photoswitchable allosteric regulation of covalent architectures within dynamic multistep cascades, which has rarely been reported before. The results resemble allosteric control within biological signaling networks and should set the stage for many endeavors, such as dynamic assemblies, molecular motors, responsive polymers, and intelligent materials.

DOI: 10.1021/jacs.4c01240

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c01240