Metal-organic framework-sealed heterogeneous nanoenzyme: A dual-mode core–shell sensor for sensitive determination of the chlorpyrifos residue in environment and bioaccumulation in food

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Switzerland : 1996), 2024-12, Vol.501, p.157693, Article 157693
• Main Authors: Liu, Jintong, Tang, Jie, Mo, Yanyang, Zhou, Lin, Cai, Tingting, Yang, Hong
• Format: Article
• Language: English
• Subjects: Bioaccumulation; Chlorpyrifos; Dual-mode sensor; Metal-organic framework; Nanoenzyme; Pesticide residue
• ISSN: 1385-8947
• DOI: 10.1016/j.cej.2024.157693

A metal–organic framework hybrid-based nanoenzyme is developed for dual-mode sensitive detection of pesticide chlorpyrifos and its bioaccumulation. [Display omitted] •A MOF-sealed hybrid nanoenzyme system is designed for sensing pesticide chlorpyrifos.•A dual-mode sensing strategy is realized sensitively and selectively.•The sensor showed a detection limit of chlorpyrifos with 0.2 ng mL−1 by fluorescence.•The bioaccumulation of chlorpyrifos in vegetables is determined.•The strategy can be extended as a general analysis platform against pesticide. Developing efficient and intelligent method for analyzing harmful agrochemicals like organophosphorus pesticides plays a crucial role in food and environmental safety surveillance. Herein, a metal–organic framework (MOF)-sealed heterogeneous nanoenzyme was designed for monitoring the bioaccumulation of chlorpyrifos in vegetables. The hybrid named CeOx@fZIF was sequentially prepared through cerium oxide (CeOx) as the core, and Cu(II)-centered zeolitic imidazolate framework (ZIF) as shell, which encapsulated fluorescence dye. The fluorescence from the encapsulated dye and the colorimetric signal from the catalytic product by the inner nanoenzyme CeOx were synchronously blocked by the outer ZIF shell of CeOx@fZIF. Under the alkaline phosphatase (ALP) enzyme-mediated reduction of Cu(II) in the ZIF shell, the obstruction of shell was relieved with the shell collapse. The enzymatic capability of inner CeOx for colorimetric catalysis and the dye fluorescence were synergistically recovered in a controllable way. Accompanied with the chlorpyrifos-inhibited capability for ALP, a fluorescence/colorimetric dual-signal sensor was fabricated. The dual-mode signal of CeOx@fZIF-based nanosystem exhibited a strong linear correlation with chlorpyrifos concentrations, achieving the detection limit of 0.2 ng/mL in fluorescence and 15 ng/mL in colorimetric. This strategy was assessed across various food matrices and had an outstanding reaction with a high percentage of recovery. Furthermore, the nanoenzyme system was employed to determine chlorpyrifos accumulation in pakchoi. The presented nanosystem exploited the feasibility of MOF-controlled nanoenzyme sensor and lighted up a facile pathway to prepare dual-mode sensor of pesticide monitoring for food and ecological environment safety.