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Dual-ligand lanthanide metal–organic framework probe for ratiometric fluorescence detection of mercury ions in wastewater

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Abstract

By serving dipyridylic acid (DPA) and 2,5-dihydroxyterephthalic acid (DHTA) as the biligands, a novel lanthanide (Eu3+) metal–organic framework (MOF) namely Eu-DHTA/DPA was prepared for specific Hg2+ fluorescence determination. The dual-ligand approach can endows the resulting luminescent MOF with dual emission of ratiometric fluorescence and uniform size. Eu3+ produces intense red fluorescence when activated by the ligand DPA, while the other ligand DHTA produces yellow fluorescence. Under 273 nm excitation, the presence of Hg2+ in the monitoring environment causes an increase in the intensity of the DHTA fluorescence peak at 559 nm and a decrease in the intensity of the Eu3+ fluorescence peak at 616 nm. Hg2+ effectively quenches the fluorescence emission of the central metal Eu3+ in Eu-DHTA/DPA at 616 nm through a dynamic quenching effect. This recognition process occurs due to the coordination of Hg2+ with ligands such as benzene rings, carboxyl groups, and pyridine N in three-dimensional space. Hg2+ was detected by measuring the ratio between two fluorescence peaks (I559 nm/I616 nm) within the range 2—20 μM, achieving a remarkably low detection limit of 40 nM. The established ratiometric fluorescence method has been successfully applied to the determination of Hg2+ in industrial wastewater of complex composition. The method plays a crucial role in the rapid and sensitive monitoring of Hg2+ in real environmental samples. The recoveries ranged from 92.82% to 112.67% (n = 3) with relative standard deviations (RSD) below 4.8%. This study offers a convenient and effective method for constructing probes for Hg2+ monitoring, with practical applications in environmental monitoring.

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Funding

This work was financially supported by the National Natural Science Fund Regional Innovation and Development Joint Fund Project (No. U22A20617), the National Natural Science Foundation of China (22078369 and 72088101), the Innovation-Driven Project of Central South University (2023CXQD048), the Hunan Provincial Innovation Foundation for Postgraduate (No. CX20230217), and the Fundamental Research Funds for the Central Universities of Central South University (No. 2023ZZTS0135).

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, Hunan, China

    Meng Wang, Jianping Guan, Shenghong Liu, Kecen Chen, Ziyi Gao, Qi Liu & Xiaoqing Chen

  2. Key Laboratory of Hunan Province for Water Environment and Agriculture Product Safety, Central South University, Changsha, 410083, Hunan, China

    Xiaoqing Chen

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  1. Meng Wang
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  2. Jianping Guan
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Contributions

Meng Wang: Conceptualization, Methodology, Investigation, Writing—original draft preparation; Jianping Guan: Investigation, Data curation. Shenghong Liu: Investigation; Kecen Chen: Investigation; Ziyi Gao: Investigation; Qi Liu: Conceptualization, Writing—review and editing, Funding acquisition, Project administration; Xiaoqing Chen: Project administration, Funding acquisition.

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Correspondence to Qi Liu.

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Wang, M., Guan, J., Liu, S. et al. Dual-ligand lanthanide metal–organic framework probe for ratiometric fluorescence detection of mercury ions in wastewater. Microchim Acta 190, 359 (2023). https://doi.org/10.1007/s00604-023-05944-3

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