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Au/CeO<sub>2</sub> NR Restricted Inside Cu-MOFs: A Three-in-One Artificial Enzyme with Synergistically Enhanced Peroxidase-Like Activity for Dual-Mode Sensing of Multiple Biomarkers

Panpan Chen, Yan Peng, Lin Lan, Yaoyao Yuan, Jie Chen, Jinling Mo, Jiayi Miao, Hongliang He, Yang Jin, Liying Zhang, Shuhu Du

2023ACS Sustainable Chemistry & Engineering22 citationsDOI

Abstract

Nanomaterials with inherent enzyme-mimetic properties have been extensively studied in biosensing field, but it is still challenging to overcome their natively weak enzyme-mimetic activity and further promote their stabilities. In this work, a three-in-one artificial enzyme with synergistically enhanced peroxidase-like activity and outstanding stability is constructed by restricting Au-loaded CeO 2 nanorods (NR) (1% Au:CeO 2 mass ratio) inside Cu-based metal–organic frameworks (Cu(PABA)), termed Au 1 /CeO 2 NR@Cu(PABA). It has been demonstrated that the artificial enzyme possesses significantly improved performance in catalytic decomposition of H 2 O 2, with ∼2.41 and ∼1.49 times higher activity than its individual constituents (Au 1 /CeO 2 NR and Cu(PABA)), benefiting from the synergistic effect and the unique restricted structure; owns strong affinities to substrates, with separately ∼8.21- and ∼3.13-fold lower Michaelis constants toward H 2 O 2 and o -phenylenediamine, respectively, than horseradish peroxidase; and exhibits desirable pH (4–12), thermal (30–80 °C), organic solvent ( N, N -dimethylformamide, acetone, methanol, etc.), and long-term storage (30 days) stabilities, advantaging practical applications. Taking aforementioned superior properties of Au 1 /CeO 2 NR@Cu(PABA), a universal colorimetric/fluorometric dual-mode sensing platform is built and utilized for detection of biomarkers (e.g., glucose, galactose, and cholesterol) in biological fluids with satisfactory recoveries (90.2–108%). This work offers new horizons in designing high-efficiency, stable, and credible biomimetic catalysts to accelerate future advanced engineering of nanozymes.

Topics & Concepts

Artificial enzymeChemistryHorseradish peroxidaseNanomaterialsCatalysisBiosensorDimethylformamidePeroxidaseAcetoneNanotechnologyMethanolCombinatorial chemistrySolventChemical engineeringEnzymeMaterials scienceOrganic chemistryBiochemistryEngineeringAdvanced Nanomaterials in CatalysisElectrochemical sensors and biosensorsAdvanced biosensing and bioanalysis techniques