2025-09-19 東京大学
触媒による自己集合体の収率の劇的な向上
＜関連情報＞
- https://www.c.u-tokyo.ac.jp/info/news/topics/20250919140000.html
- https://www.cell.com/chem/abstract/S2451-9294(25)00332-8
超分子反応ネットワークにおける可逆性・不可逆性の触媒的操作による自己組織化結果の制御 Catalytic manipulation of reversibility and irreversibility in a supramolecular reaction network to control the self-assembly outcome
Tsukasa Abe ∙ Satoshi Takahashi ∙ Runyu Chai ∙ Hirofumi Sato ∙ Shuichi Hiraoka
Chem Published:September 17, 2025
DOI:https://doi.org/10.1016/j.chempr.2025.102741
The bigger picture
Reversibility and irreversibility are opposing phenomena that do not simultaneously emerge in elementary reactions. Incorporating the advantages of reversible and irreversible reactions into a system can realize a versatile chemical system that is globally irreversible but locally reversible. Integrating reversible elementary reactions into a reaction network makes such a hybridized system possible. In this study, we obtained a metastable state in which one of the assemblies was catalytically biased by the hybridization of reversibility and irreversibility in a reversible reaction network of molecular self-assembly. Appropriate catalytic activity fine-tuned the hybridization of reversibility and irreversibility in the reaction network, leading to a kinetically biased metastable state. These results significantly advance our understanding of the complexity of reversible reaction networks and how to control them.
Highlights
- ReO4− greatly improved the yield of the M6L4 square-based pyramid (SP)
- This result was analyzed in a reversible reaction network model
- The efficient acceleration of certain reaction steps led to high SP yields
- Local reaction loops retain the metastable state of high SP yield
Summary
Catalysis is a key strategy for enhancing the yields and selectivities of desired products in both living systems and industry. Catalysts do not affect the reaction outcome of simple reversible reactions; they only accelerate equilibration. Herein, we report that catalysis greatly improves the self-assembly yield. In the presence of ReO4− as the catalyst, the M6L4 square-based pyramid (SP) was almost quantitatively assembled, whereas the yield was only 24% without catalysis. Experimental and theoretical analyses of the self-assembly revealed that M3L3 and M4L3 triangle species were trapped without ReO4−, that in the presence of the catalyst, the conversion of the trapped species was indirectly promoted by greater acceleration of the late stage of the self-assembly, and that local reaction loops involving SP prevented global equilibration to attain a metastable state.
