Porous double variable-valence FeCe nanozyme: preparation, catalytic mechanism, and use as sensor array for high-throughput discrimination of heavy metal ions

Abstract

A porous double variable-valence FeCe nanozyme (pFeCezyme) was designed using hemoglobin as template and Fe-source. pFeCezyme exhibited excellent peroxidase (POD)-like activity due to the porous structure, maximized exposure of active sites, synergy of double variable-valence metals, and enhanced electron transfer between Fe and Ce. The POD-like activity can be quenched (off) by L-cysteine (L-Cys) and then restored (on) by adding of heavy metal ions (HMIs). The degree effect of "on-off" POD-like activity can be varied by changing pH conditions. Therefore, a three-channels pFeCezyme sensor array was established using pH values (pH = 4.0, 5.0, and 6.0) as sensing elements. Interestingly, pFeCezyme sensor array can generate distinct colorimetric fingerprints due to the different affinity ability between L-Cys and HMIs. The pFeCezyme sensor array was successfully applied to highly sensitive and high throughput discrimination of HMIs (Ag⁺, Hg²⁺, Cu²⁺, Cr⁶⁺, and Fe³⁺) even at low concentration of 0.1 μM. Meanwhile, The pFeCezyme sensor array can rapidly distinguish binary and ternary mixed HMIs within 10 min, and the HMIs and interfering substances can be well discriminated. Furthermore, the pFeCezyme sensor array could effectively distinguished HMIs in real samples with an excellent identification for unknow HMIs. This research provides a novel strategy for identifying a variety of HMIs, which exhibits a broad application prospect in HMIs monitoring.

Keywords: Colorimetric sensor array; Double variable-valence; FeCe nanozyme; Heavy metal ions.