Chemical Research in Chinese Universities ›› 2024, Vol. 40 ›› Issue (3): 499-507.doi: 10.1007/s40242-024-4043-3

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Elaborate Design of Two Novel Fluorescent Zinc-based Metal-Organic Frameworks for Highly Efficient Tetracycline Antibiotics Detection

TAO He, JI Chengshan, ZHANG Jian, YIN Yuanyuan, JIA Wenwen, JIANG Xin, XU Jie, YANG Yulin   

  1. MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, P. R. China
  • Received:2024-02-27 Online:2024-06-01 Published:2024-06-01
  • Contact: ZHANG Jian,E-mail:zhaji@hit.edu.cn E-mail:zhaji@hit.edu.cn
  • Supported by:
    This work was supported by the National Natural Science Foundation of China (Nos. 22072034 and 22001050).

Abstract: The abuse of tetracycline antibiotics has caused great harm to human health and ecosystems. Developing inexpensive, convenient and sensitive methods for the detection of tetracycline antibiotics is highly desirable. Herein, based on the H4ddp ligand [H4ddp=3-(3,5-dicarboxyphenyl) pyridine-2,6-dicarboxylic acid], two novel zinc-based metal-organic frameworks (MOFs) {[Zn3(ddp)2(H2O)4]·3H2O}n (Zn1-ddp) and {[Zn3(ddp)2(H2O)4]·3H2O}n (Zn2-ddp) were successfully designed by delicate structural regulation. Both Zn1-ddp and Zn2-ddp exhibited excellent water and chemical stability and showed excellent fluorescence quenching performance for tetracycline antibiotics. Notably, the more advanced framework structure and better fluorescent performance make Zn1-ddp more sensitive than Zn2-ddp in fluorescent detection with a detection limit of 0.29 μmol/L for tetracycline (TC), 0.09 μmol/L for doxycycline (DOX), 0.10 μmol/L for minocycline (MIN) and metacycline (MEL), 0.19 μmol/L for chlortetracycline (CTC), and 0.67 μmol/L for oxytetracycline (OTC) among tetracycline antibiotics. The fluorescence quenching mechanism of Zn1-ddp and Zn2-ddp for tetracycline antibiotics detection was deeply investigated. The reasons for the superior detection performance of Zn1-ddp over Zn2-ddp were also analyzed in depth through Fourier transform infrared spectrophotometry (FTIR), X-ray photoelectron spectroscopy (XPS) analysis and framework structure analysis. The developed method opens up a new perspective for antibiotics detection based on zinc-based MOFs.

Key words: Water system, Metal-organic framework, Fluorescent detection, Tetracycline antibiotic