Atomically Site Synergistic Effects of Dual-Atom Nanozyme Enhances Peroxidase-like Properties

Abstract

Pursuing effective and generalized strategies for modulating the electronic structures of atomically dispersed nanozymes with remarkable catalytic performance is exceptionally attractive yet challenging. Herein, we developed a facile “formamide condensation and carbonization” strategy to fabricate a library of single-atom (M1-NC; 6 types) and dual-atom (M1/M2-NC; 13 types) metal-nitrogen-carbon nanozymes (M = Fe, Co, Ni, Mn, Ru, Cu) to reveal peroxidase- (POD-) like activities. The Fe1Co1-NC dual-atom nanozyme with Fe1-N4/Co1-N4 coordination displayed the highest POD-like activity. Density functional theory (DFT) calculations revealed that the Co atom site synergistically affects the d-band center position of the Fe atom site and served as the second reaction center, which contributes to better POD-like activity. Finally, Fe1Co1 NC was shown to be effective in inhibiting tumor growth both in vitro and in vivo, suggesting that diatomic synergy is an effective strategy for developing artificial nanozymes as novel nanocatalytic therapeutics.

An emerging direction for nanozyme design: from single-atom to dual-atomic-site catalysts

“…Song's group further illuminated the synergistic effect observed in Fe 1 Co 1 –NC dual-atom POD-like nanozymes. 91 This work revealed that the incorporation of heteronuclear metal sites induced electronic structure modulation and optimized H 2 O 2 substrate adsorption (Fig. 6d).…”

“…5d). 91 The Fe 1 Co 1 –NC dual-atom nanozyme with Fe 1 –N 4 /Co 1 –N 4 coordination exhibited remarkable enhancement of POD-like catalytic properties and excellent photothermal conversion efficiency. Wei's group presented a facile approach for crafting Zn/Mo dual atomic-based SAzymes (Zn/Mo DSAC–SMA) via the assembly of supramolecular coordination complexes and polyoxometalates (Fig.…”

Ultrasensitive fluorescence immunoassay of pepsinogen I based on enzyme-triggered decomposition of AuNCs/MnO2

“…35–37 Meanwhile, two characteristic peaks occurred at 653.96 and 642.56 eV, attributed to the Mn 2p 3/2 and Mn 2p 1/2 spin orbitals of MnO 2 , respectively. 38–40 Notably, the appearance of the N 1s peak correlates with BSA.…”

Ultrasensitive electrochemical detection of uric acid based on cobalt-embedded nitrogen-doped carbon

“…In recent years, with the advancement of nanotechnology and diagnostic techniques, different signal transduction strategies based on nanomaterials are playing a great role in biomolecular diagnostics such as electrochemical methods, photoelectrochemical methods, fluorescence methods, piezoresistive sensing, etc. [7][8][9][10][11][12] Among various techniques, classical electrochemical analysis, developed by integrating electronic signalers/converters and identifiers, has gained a unique role in the field of analytical detection due to the obvious advantages of great sensitivity, fast response, ease of operation, and compactness. [13][14][15] In the last few decades, a large number of electrochemical sensors have been successfully designed and developed as powerful tools to interrogate the expression levels of target objects ranging from ions to disease biomarkers, pesticides, and biotoxins in real samples.…”