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Preparation of complex biological sample-compatible “turn-on”-type ratiometric fluorescent molecularly imprinted polymer microspheres via one-pot surface-initiated ATRP

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Abstract

The efficient preparation of ratiometric fluorescent molecularly imprinted polymer (MIP) microspheres that can directly and selectively optosense a herbicide (i.e., 2,4-dichlorophenoxyacetic acid, 2,4-D) in undiluted pure milk is described. The dual fluorescent MIP microparticles were readily obtained through grafting a green 4-nitrobenzo[c][1,2,5]oxadiazole (NBD)-labeled 2,4-D-MIP layer with hydrophilic polymer brushes onto the preformed uniform “living” red CdTe quantum dot (QD)-labeled SiO2 microspheres via one-pot surface-initiated atom transfer radical polymerization (SI-ATRP) in the presence of a polyethylene glycol macro-ATRP initiator. They proved to be highly promising “turn-on”-type fluorescent chemosensors with red CdTe QD (the maximum emission wavelength λe,max around 710 nm) and green NBD (λe,max around 515 nm) as the reference fluorophore and “turn-on”-type responsive fluorophore, respectively. The sensors showed excellent photostability and reusability, high 2,4-D selectivity and sensitivity (the limit of detection = 0.12 μM), and direct visual detection ability (a fluorescent color change occurs from red to blue-green with the concentration of 2,4-D increasing from 0 to 100 μM) in pure bovine milk. The sensors were used for 2,4-D detection with high recoveries (96.0–104.0%) and accuracy (RSD ≤ 4.0%) in pure goat milk at three spiking levels of both 2,4-D and its mixtures with several analogues. This new strategy lays the foundation for efficiently developing diverse complex biological sample-compatible ratiometric fluorescent MIPs highly useful for real-world bioanalyses and diagnostics.

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Funding

This work was financially supported by the National Natural Science Foundation of China (21574070 and 22071121) and the Project supported by the NCC Fund (NCC2020PY12).

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Authors and Affiliations

  1. State Key Laboratory of Medicinal Chemical Biology, Key Laboratory of Functional Polymer Materials (Ministry of Education), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin, 300071, China

    Qun Li, Wanlan Zhang, Xinru Liu & Huiqi Zhang

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  1. Qun Li
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  2. Wanlan Zhang
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  3. Xinru Liu
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Correspondence to Huiqi Zhang.

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Li, Q., Zhang, W., Liu, X. et al. Preparation of complex biological sample-compatible “turn-on”-type ratiometric fluorescent molecularly imprinted polymer microspheres via one-pot surface-initiated ATRP. Microchim Acta 189, 464 (2022). https://doi.org/10.1007/s00604-022-05551-8

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