Bioinspired catalysis: Engineering microenvironment from chemical to spatial confinement

Abstract

Enzymes’ active sites reside within precisely tuned chemical microenvironments that stabilize transition states, while sophisticated spatial architectures regulate substrate access and intermediate transport. Replicating this complexity in artificial systems, however, remains a significant challenge. In this perspective, we examine recent advances in chemical or spatial confinement, summarizing their performance-enhancing mechanisms. Specifically, we highlight the synergy between these two effects, starting with synthetic enzyme mimics, followed by a focus on material-microbial and electro-microbial hybrid systems. Furthermore, we introduce a rational design of confinement strategies by analyzing the specific bottlenecks in catalytic systems. Finally, based on the analysis of the synergistic confinement, we envision the further extension to chemo-biological hybrid catalysis. Our vision is to integrate chemical and spatial confinement within a unified architecture for developing high-performance bioinspired catalytic systems, having the merits of low energy consumption, high selectivity, and high flux.