Manganese-doped iron coordination polymer nanoparticles with enhanced peroxidase-like activity for colorimetric detection of antioxidants

Abstract

A convenient and sensitive antioxidant assay with high performance is essential for assessing food quality and monitoring the oxidative stress level of biological matrices. Although coordination polymer nanoparticles (CPNs)-based nanozymes have emerged as candidates in the analytical field, strategies to improve the catalytic activity of CPNs have been scarcely revealed and studied. Herein, we demonstrate a manganese (Mn) doping strategy to enhance the peroxidase-mimetic activity of Fe-based CPNs. By tuning the Mn doping amounts and selecting 2,5-dihydroxyterephthalic acid (H₄DHTP) as ligands, the produced nanozymes in amorphous state followed the catalytic activity order of Fe₅Mn-DHTP > Fe₈Mn-DHTP > Fe₂Mn-DHTP > Fe-DHTP > Mn-DHTP. Ulteriorly, benefitting from the best catalytic performance and definite catalytic mechanism of Fe₅Mn-DHTP, versatile colorimetric assays for ultrasensitive detection of one exogenous antioxidant (ascorbic acid, AA) and two endogenous antioxidants (glutathione, GSH; cysteine, Cys) have been deftly devised based on the inhibition of the 3,3′,5,5′-tetramethylbenzidine chromogenic reaction in presence of H₂O₂. It was found that mercaptan (GSH and Cys) and AA exhibited different inhibition mechanisms. Practically, such a colorimetric assay was viable to determine the total antioxidant capacity of drugs and foods with desirable results. This work proposes a feasible strategy for embellishing CPN nanozymes used for designing sensitive and convenient assays for various antioxidants based on an explicit detection mechanism.