韩国科学技术院Ihee, Hyotcherl团队报道了用飞秒连续晶体学捕获的金属有机框架的动态三维结构。相关研究成果发表在2024年3月25日出版的国际学术期刊《自然—化学》。

由小分子构建块组成的结晶体系已成为具有多种应用前景的材料。不仅要表征它们的静态结构，还要表征它们的结构对外部刺激的转换，这一点非常重要。飞秒时间分辨晶体学有可能探测结构转变的实时动力学，但到目前为止，这还没有在非生物晶体中的化学反应中实现。

该文中，研究人员将时间分辨串行飞秒晶体学（TR-SFX）（一种强大的蛋白质结构动力学可视化技术），应用于由铁卟啉和六锆节点组成的金属-有机框架，并阐明了其结构动力学。从TR-SFX数据导出的时间分辨电子密度图揭示了三分叉结构路径：Zr和Fe原子的相干振荡运动，Fe卟啉和Zr6节点分别经历隆起和无序运动的瞬态结构，以及具有各向同性结构无序的振动热结构。这些发现证明了TR-SFX研究化学系统的可行性。

附：英文原文

Title: Dynamic three-dimensional structures of a metal–organic framework captured with femtosecond serial crystallography

Author: Kang, Jaedong, Lee, Yunbeom, Lee, Seonggon, Ki, Hosung, Kim, Jungmin, Gu, Jain, Cha, Yongjun, Heo, Jun, Lee, Kyung Won, Kim, Seong Ok, Park, Jaehyun, Park, Sang-Youn, Kim, Sangsoo, Ma, Rory, Eom, Intae, Kim, Minseok, Kim, Jeongho, Lee, Jae Hyuk, Ihee, Hyotcherl

Issue&Volume: 2024-03-25

Abstract: Crystalline systems consisting of small-molecule building blocks have emerged as promising materials with diverse applications. It is of great importance to characterize not only their static structures but also the conversion of their structures in response to external stimuli. Femtosecond time-resolved crystallography has the potential to probe the real-time dynamics of structural transitions, but, thus far, this has not been realized for chemical reactions in non-biological crystals. In this study, we applied time-resolved serial femtosecond crystallography (TR-SFX), a powerful technique for visualizing protein structural dynamics, to a metal–organic framework, consisting of Fe porphyrins and hexazirconium nodes, and elucidated its structural dynamics. The time-resolved electron density maps derived from the TR-SFX data unveil trifurcating structural pathways: coherent oscillatory movements of Zr and Fe atoms, a transient structure with the Fe porphyrins and Zr6 nodes undergoing doming and disordering movements, respectively, and a vibrationally hot structure with isotropic structural disorder. These findings demonstrate the feasibility of using TR-SFX to study chemical systems.

DOI: 10.1038/s41557-024-01460-w

Source: https://www.nature.com/articles/s41557-024-01460-w