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Ce-MOF with Intrinsic Haloperoxidase-Like Activity for Ratiometric Colorimetric Detection of Hydrogen Peroxide.

ABSTRACT: Metal-organic framework (MOF) nanozymes, as emerging members of the nanozymes, have received more and more attention due to their composition and structural characteristics. In this work, we report that mixed-valence state Ce-MOF (MVCM) has intrinsic haloperoxidase-mimicking activity. MVCM was synthesized by partial oxidation method using Ce-MOF as a precursor. In the presence of H₂O₂ and Br^-, MVCM can catalyze oxidative bromination of chromogenic substrate phenol red (PR) to produce the blue product bromophenol blue (Br₄PR), showing good haloperoxidase-like activity. Because of the special chromogenic substrate, we constructed a ratiometric colorimetric-sensing platform by detecting the absorbance of the MVCM-(PR, Br^-) system at wavelengths of 590 and 430, for quantifying H₂O₂, where the detection limit of the H₂O₂ is 3.25 μM. In addition, the haloperoxidase-mimicking mechanism of the MVCM is proposed. Moreover, through enzyme kinetics monitoring, the K_m (H₂O₂ and NH₄Br) of the MVCM is lower than that of cerium oxide nanomaterials, indicating that the MVCM has a stronger binding affinity for H₂O₂ and NH₄Br than other materials. This work provides more application prospects for the development of nanozymes in the field of biosensors in the future.

SUBMITTER: Cheng Y

PROVIDER: S-EPMC8301872 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Hydrogen peroxide (H2O2) is commonly used as an oxidizing, bleaching, or antiseptic agent. It is also hazardous at increased concentrations. It is therefore crucial to monitor the presence and concentration of H2O2, particularly in the vapor phase. However, it remains a challenge for many state-of-the-art chemical sensors (e.g., metal oxides) to detect hydrogen peroxide vapor (HPV) because of the interference of moisture in the form of humidity. Moisture, in the form of humidity, is guaranteed to be present in HPV to some extent. To meet this challenge, herein, we report a novel composite material based on poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) doped with ammonium titanyl oxalate (ATO). This material can be fabricated as a thin film on electrode substrates for use in chemiresistive sensing of HPV. The adsorbed H2O2 will react with ATO, causing a colorimetric response in the material body. Combining colorimetric and chemiresistive responses resulted in a more reliable dual-function sensing method that improved the selectivity and sensitivity. Moreover, the composite film of PEDOT:PSS-ATO could be coated with a layer of pure PEDOT via in situ electrochemical synthesis. The pure PEDOT layer was hydrophobic, shielding the sensor material underneath from coming into contact with moisture. This was shown to mitigate the interference of humidity when detecting H2O2. A combination of these material properties makes the double-layer composite film, namely PEDOT:PSS-ATO/PEDOT, an ideal sensor platform for the detection of HPV. For example, upon a 9 min exposure to HPV at a concentration of 1.9 ppm, the electrical resistance of the film increased threefold, surpassing the bounds of the safety threshold. Meanwhile, the colorimetric response observed was 2.55 (defined as the color change ratio), a ratio at which the color change could be easily seen by the naked eye and quantified. We expect that this reported dual-mode sensor will find extensive practical applications in the fields of health and security with real-time, onsite monitoring of HPV.

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Ce-MOF with Intrinsic Haloperoxidase-Like Activity for Ratiometric Colorimetric Detection of Hydrogen Peroxide.

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