Colorimetric detection of tetracycline by enhancing peroxidase-like activity of polymerized MnO2@ZIF-67 nanocomposites

Yahan Cui; Niao Zhao; Shenghui Wang; Hongyuan Yan; Dandan Han

doi:10.1016/j.bios.2025.117726

Colorimetric detection of tetracycline by enhancing peroxidase-like activity of polymerized MnO₂@ZIF-67 nanocomposites

Biosens Bioelectron. 2025 Jun 21:287:117726. doi: 10.1016/j.bios.2025.117726. Online ahead of print.

Authors

Yahan Cui¹, Niao Zhao¹, Shenghui Wang¹, Hongyuan Yan², Dandan Han³

Affiliations

¹ Hebei Key Laboratory of Public Health Safety, School of Public Health, Hebei University, Baoding, 071002, China.
² Hebei Key Laboratory of Public Health Safety, School of Public Health, Hebei University, Baoding, 071002, China; State Key Laboratory of New Pharmaceutical Preparations and Excipients, Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of Ministry of Education, College of Chemistry and Materials Science, Hebei University, Baoding, 071002, China. Electronic address: yanhy@hbu.edu.cn.
³ Hebei Key Laboratory of Public Health Safety, School of Public Health, Hebei University, Baoding, 071002, China. Electronic address: hdd@hbu.edu.cn.

PMID: 40580739
DOI: 10.1016/j.bios.2025.117726

Abstract

Concerns regarding the hazard of the antibiotic tetracycline (TC) have driven the attempt to exploit efficient, straightforward, and economic assays for warning early food safety and environmental security. Here, we report the development of MnO₂@ZIF-67@MAA colorimetric sensor, which was constructed by polymerization reaction using manganese dioxide (MnO₂) nanomaterials modified by metal-organic framework (ZIF-67) as support carriers and catalysts for the rapid detection and determination of TC. The MnO₂@ZIF-67@MAA has peroxidase-like activity and catalyzed the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H₂O₂ to produce blue oxTMB. TC can react specifically with the MnO₂@ZIF-67@MAA active site to promote the further reaction of catalytic substrates TMB and H₂O₂ with the inside catalytic center of MnO₂@ZIF-67@MAA, resulting in the transformation enhancement of TMB into oxTMB, yielding a TC concentration-dependent in colorimetric increases. A colorimetric method based on MnO₂@ZIF-67@MAA was developed for the rapid detection of TC in medical wastewater and fresh milk samples. The sensor platform has high sensitivity and selectivity for TC detection, with the detection limit as low as 0.025 μM. These results reveal the great potential of MnO₂@ZIF-67@MAA for environmental chemistry and food chemical sensing applications.

Keywords: Colorimetric sensor; Metal oxide nanozymes; Metal-organic frameworks; Surface functionalization; Tetracycline.