van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands.
Angew Chem Int Ed Engl. 2023 Apr 11;62(16):e202218162. doi: 10.1002/anie.202218162. Epub 2023 Mar 8.
Metabolic pathways are highly regulated by effector molecules that influences the rate of enzymatic reactions. Inspired by the catalytic regulation found in living cells, we report a Pt L cage of which the activity can be controlled by effectors that bind inside the cage. The cage shows catalytic activity in the lactonization of alkynoic acids, with the reaction rates dependent on the effector guest bound in the cage. Some effector guests enhance the rate of the lactonization by up to 19-fold, whereas one decreases it by 5-fold. When mixtures of specific substrates are used, both starting materials and products act as guests for the Pt L cage, enhancing its catalytic activity for one substrate while reducing its activity for the other. The reported regulatory behavior obtained by the addition of effector molecules paves the way to the development of more complex, metabolic-like catalyst systems.
代谢途径受到效应分子的高度调节,这些分子影响酶反应的速率。受活细胞中发现的催化调节的启发,我们报告了一种 Pt L 笼,其活性可以通过结合在笼内的效应物来控制。该笼在炔酸的内酯化反应中表现出催化活性,反应速率取决于笼内结合的效应物客体。一些效应物客体可将内酯化的速率提高 19 倍,而有一种则降低 5 倍。当使用特定的混合底物时,起始材料和产物都可作为 Pt L 笼的客体,从而增强其对一种底物的催化活性,同时降低其对另一种底物的活性。通过添加效应分子获得的报道的调节行为为开发更复杂的、类似代谢的催化剂系统铺平了道路。