摘要
Highly evolved multi-enzyme cascade catalytic reactions in organisms facilitate rapid transfer of substrates and efficient conversion of intermediates in the catalytic unit,thus rationalizing their efficient biocatalysis.In this study,pore-ordered mesoporous single-atom(Fe)nitrogen-doped carbon nanoreactors(Mp-Fe-CN)were designed,in which a reasonable pore size was designed as a natural enzyme trap coupled to a simulated enzyme center.A polarity-mediated strategy was developed to obtain atomically dispersed nanoporous substrates,with the finding that polarity-guided engineering of the nitrogen-ligand environment and vacancy cluster defects clearly affects nanoporous activity,accompanied by appreciable mesoporous pore size elevation.The active center and distal N atom coordination of Fe-N_(4) affect the catalytic process of the nanozyme exposed by density functional theory(DFT),determining the contribution of hybridized orbitals to electron transfer and the decisive step.A cascade nanoreactor-based domain-limited sarcosine oxidase developed for non-invasive monitoring of sarcosine levels in urine for evaluation of potential prostate carcinogenesis as a proof of concept.Based on the design of surface mesoporous channels of nanocatalytic units,a bridge was built for the interaction between nanozymes and natural enzymes to achieve cascade nanocatalysis of natural enzymatic products.
基金
supported by the National Natural Science Foundation of China(Nos.22274022,21874022 and 21675029).
