Decoding and quantitative detection of antibiotics by a luminescent mixed-lanthanide-organic framework

doi:10.1007/s11783-022-1589-5

Front. Environ. Sci. Eng.

2022, Vol. 16

Issue (12) : 154 https://doi.org/10.1007/s11783-022-1589-5

RESEARCH ARTICLE

Decoding and quantitative detection of antibiotics by a luminescent mixed-lanthanide-organic framework

Yuping Wang¹, Jing Xia², Yanxin Gao¹(

)

¹. Department of Environmental Science and Engineering, Fuzhou University, Minhou 350108, China
². State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China

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Abstract

● A series of mixed-LOFs and portable LOF-fibers were synthesized.

● LOF-S3 was selected as a luminescent sensor for antibiotics.

● Mixed-LOF was capable of decoding antibiotics by emission intensity ratios.

● Linear relationship between antibiotic concentration and I545nm/I618nm was observed.

Due to the potential risk of antibiotics to the environment, the development of inexpensive, simple, and reliable antibiotic detection methods is significant but also faces challenges. In this work, several lanthanide-organic frameworks (LOFs), constructed from lanthanide ions (Eu³⁺ and/or Tb³⁺) and 1,3,5-benzene-tricarboxylic acid (BTC), were synthesized by solvothermal method. LOF-S3 with comparable emission peaks of ⁵D₄ → ⁷F₅ (Tb³⁺, 545 nm) and ⁵D₀ → ⁷F₂ (Eu³⁺, 618 nm) was selected as a luminescent sensor. In this system, the highly efficient energy transferred from the organic linker to lanthanide ions and from Tb³⁺ to Eu³⁺ occurs. LOF-S3 sensor was capable of decoding antibiotics by distinguishable emission intensity ratios. Therefore, a two-dimensional decoded map of antibiotics was established. The linear relationship between antibiotic concentration and emission intensity ratio indicated the quantitative determination of antibiotics was feasible. As a typical analyte, the response mechanism of nalidixic acid (NA) was investigated in detail. The competition of NA and BTC for UV light absorption, as well as the binding propensity of NA and Tb, affected the organic linkers-to-lanthanide ions and Tb-to-Eu energy transfer, resulting in the change of fluorescence intensity ratio. The self-calibrating mixed-LOF sensor overcame the uncontrollable errors of the traditional absolute emission intensity method and generated stable luminescent signals in multiple cycles. Furthermore, the integration of LOF-S3 with polymer fibers enabled the formation of a LOF-polymer fibrous composite with fluorescence detection capability, which is a promising portable sensor for practical applications.

Keywords Antibiotics Sensor Luminescence Lanthanide-organic frameworks

Corresponding Author(s): Yanxin Gao

Issue Date: 15 June 2022

Cite this article:

Yuping Wang,Jing Xia,Yanxin Gao. Decoding and quantitative detection of antibiotics by a luminescent mixed-lanthanide-organic framework[J]. Front. Environ. Sci. Eng., 2022, 16(12): 154.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-022-1589-5
https://academic.hep.com.cn/fese/EN/Y2022/V16/I12/154

Fig.1 (a) XRD spectra of Ln-BTC; (b) the coordination state of the Ln ion and the structure of Ln-BTC (Tb and/or Eu, blue; O, red; C, gray); (c) fluorescence microscope photograph of mixed-Ln-BTC; (d) SEM image of mixed-Ln-BTC.

Fig.2 Emission spectra for (a) Tb(NO₃)₃·6H₂O and Tb-BTC, (b) Eu(NO₃)₃·6H₂O and Eu-BTC.

Fig.3 (a) Luminescent spectra of Ln-BTCs (λ_ex = 286 nm) in the solid-state at room temperature; (b) the optical photographs for LOF samples under fluorescence microscope; (c) CIE chromaticity coordinates.

Fig.4 (a) Emission spectra and (b) intensity ratios (I_{545 nm}/I_{618 nm}) of LOF-S3 after the adsorption of antibiotics (λ_ex = 286 nm).

Fig.5 (a) Emission spectra and (b) emission intensity ratios (I_{545 nm}/I_{618 nm}) of LOF-S3 after the adsorption of sulfonamide antibiotics (λ_ex = 286 nm).

Fig.6 Decoded map for different antibiotics of LOF-S3 sensor (λ_ex = 286 nm, R₁ = I_{545 nm}/I_{618 nm} of the antibiotic, R₂ = I_592nm/I_488nm of the antibiotic, R_L1 = I_{545 nm}/I_{618 nm} of LOF-S3, R_L2 = I_592nm/I_488nm of LOF-S3).

Fig.7 (a) Intensity ratios (I_{545 nm}/I_{618 nm}) of LOF-S3 in the presence of different concentrations of nalidixic acid (λ_ex = 286 nm); (b) Emission spectra of LOF-S3 before and after the detection of nalidixic acid; (c) possible mechanism of LOF-S3 sensing for nalidixic acid.

Fig.8 Recycling probing of nalidixic acid by LOF-S3: the integrated emission intensity ratios (I_{545 nm}/I_{618 nm}) after adsorption and desorption of nalidixic acid (200 mL 100 μmol/L nalidixic acid solution, 5 mg Ln-BTC,λ_ex = 286 nm).

Fig.9 (a) Images and (b) luminescence spectra of LOF-S3 fibers; (c) the optical photographs for mixed-LOF fibers under fluorescence microscope before and after the detection of nalidixic acid (NA 1: 50 μmol/L, NA 2: 100 μmol/L, NA 3: 200 μmol/L); (d) Schematic diagram for the detection of antibiotics using a smartphone.

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