Issue 41, 2020

Construction of a chiral artificial enzyme used for enantioselective catalysis in live cells

Abstract

Nanozymes as a newcomer in the artificial enzyme family have shown several advantages over natural enzymes such as their high stability in harsh environments, facile production on large scale, long storage time, low costs, and higher resistance to biodegradation. However, compared with natural enzymes, it is still a great challenge to design a nanozyme with high selectivity, especially high enantioselectivity. It is highly desirable and demanding to develop chiral nanozymes with high and on-demand enantioselectivity for practical applications. Herein, we present an unprecedented approach to construct chiral artificial peroxidase with ultrahigh enantioselectivity. Inspired by the structure of the natural enzyme horseradish peroxidase (HRP), we have constructed a series of stereoselective nanozymes (Fe3O4@Poly(AA)) by using the ferromagnetic nanoparticle (Fe3O4 NP) yolk as the catalytic core and amino acid-appended chiral polymer shell as the chiral selector. Among them, Fe3O4@Poly(D-Trp) exhibits the highest enantioselectivity. More intriguingly, their enantioselectivity will be readily reversed by replacing D-Trp with L-Trp. The selectivity factor is up to 5.38, even higher than that of HRP. Kinetic parameters, dialysis experiments, and molecular simulations together with activation energy reveal that the selectivity originates from the D-/L-Trp appended polymer shell, which can result in better affinity and catalytic activity to D-/L-tyrosinol. The artificial peroxidases have been used for asymmetric catalysis to prepare enantiopure D- or L-enantiomers. Besides, by using fluorescent labelled FITC-tyrosinolL and RhB-tyrosinolD, the artificial peroxidases can catalyze green or red fluorescent chiral tyrosinol to selectively label live yeast cells among yeast, S. aureus, E. coli and B. subtilis bacterial cells. This work opens a new avenue for better design of stereoselective artificial enzymes.

Graphical abstract: Construction of a chiral artificial enzyme used for enantioselective catalysis in live cells

Supplementary files

Article information

Article type
Edge Article
Submitted
02 iyn 2020
Accepted
22 sen 2020
First published
23 sen 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2020,11, 11344-11350

Construction of a chiral artificial enzyme used for enantioselective catalysis in live cells

Y. Zhou, W. Wei, F. Cui, Z. Yan, Y. Sun, J. Ren and X. Qu, Chem. Sci., 2020, 11, 11344 DOI: 10.1039/D0SC03082A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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