Real-time observation of a metal complex-driven reaction intermediate using a porous protein crystal and serial femtosecond crystallography

Author:

Maity BasudevORCID,Shoji MitsuoORCID,Luo Fangjia,Nakane TakanoriORCID,Abe Satoshi,Owada Shigeki,Kang JungminORCID,Tono KensukeORCID,Tanaka RieORCID,Pham Thuc ToanORCID,Kojima MarikoORCID,Hishikawa YukiORCID,Tanaka Junko,Tian Jiaxin,Nagama Misaki,Suzuki Taiga,Noya Hiroki,Nakasuji Yuto,Asanuma Asuka,Yao Xinchen,Iwata So,Shigeta YasuteruORCID,Nango ErikoORCID,Ueno TakafumiORCID

Abstract

AbstractDetermining short-lived intermediate structures in chemical reactions is challenging. Although ultrafast spectroscopic methods can detect the formation of transient intermediates, real-space structures cannot be determined directly from such studies. Time-resolved serial femtosecond crystallography (TR-SFX) has recently proven to be a powerful method for capturing molecular changes in proteins on femtosecond timescales. However, the methodology has been mostly applied to natural proteins/enzymes and limited to reactions promoted by synthetic molecules due to structure determination challenges. This work demonstrates the applicability of TR-SFX for investigations of chemical reaction mechanisms of synthetic metal complexes. We fix a light-induced CO-releasing Mn(CO)3 reaction center in porous hen egg white lysozyme (HEWL) microcrystals. By controlling light exposure and time, we capture the real-time formation of Mn-carbonyl intermediates during the CO release reaction. The asymmetric protein environment is found to influence the order of CO release. The experimentally-observed reaction path agrees with quantum mechanical calculations. Therefore, our demonstration offers a new approach to visualize atomic-level reactions of small molecules using TR-SFX with real-space structure determination. This advance holds the potential to facilitate design of artificial metalloenzymes with precise mechanisms, empowering design, control and development of innovative reactions.

Funder

MEXT | Japan Society for the Promotion of Science

Publisher

Springer Science and Business Media LLC

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