A Tb (Ⅲ) Coordination Polymer Based on 5-(2-(Pyrazole-1-yl) Pyridine-5-yl) Terephthalic Acid and Its Visual Detection of Quinolone Antibiotics
Abstract
1. Introduction
2. Experimental Section
2.1. Synthesis of [Tb(HPPIPA)(PPIPA)H2O]n (Complex 1)
2.2. X-Ray Crystal Diffraction Data of Complex 1
2.3. Fluorescence Detection Experiment
2.4. Test Strip Preparation
2.5. Fluorescent Sensing Film
3. Results and Discussion
3.1. Crystal Structure of Complex 1
3.2. Fluorescence Detection of Quinolone Antibiotics
3.3. Detection of OFX and LFX in Pretreated Commercial Milk
3.4. Visual Detection of Quinolone Antibiotics
3.5. Mechanism of Detection
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
- Lin, C.J.; Wang, H.H.; Li, T.; Zhang, Z.Y. A [Co5] cluster-based organic framework as fluorescent detection platform toward quinolone antibiotics. Appl. Organomet. Chem. 2024, 38, e7512. [Google Scholar] [CrossRef]
- Pandi, R.L.; Pandurangan, N.; Sukanya, K. Recent advances in luminescent metal–organic frameworks (LMOFs) based fluorescent sensors for antibiotics. Coord. Chem. Rev. 2021, 435, 213793. [Google Scholar] [CrossRef]
- Thu, D.M.P.; Zyta, M.Z.; Mark, A.T.B. Quinolone antibiotics. Med. Chem. Commun. 2019, 10, 1719–1739. [Google Scholar] [CrossRef]
- Li, C.H.; Xu, X.; Ji, Y.X.; Wang, F.L. Amino-functionalized Al-MOF modulated TpTt-COF with dual-emission for fluorescent and optosmart detecting tetracycline in food samples. Food Chem. 2023, 425, 136476. [Google Scholar] [CrossRef]
- Vybíralová, Z.; Nobilis, M.; Zoulova, J. High-performance liquid chromatographic determination of ciprofloxacin in plasma samples. J. Pharm. Biomed. Anal. 2005, 37, 851–858. [Google Scholar] [CrossRef]
- Xu, X.Y.; Liu, L.H.; Jia, Z.M.; Shu, Y. Determination of enrofloxacin and ciprofloxacin in foods of animal origin by capillary electrophoresis with field amplified sample stacking-sweeping technique. Food Chem. 2015, 176, 219–225. [Google Scholar] [CrossRef]
- Pascual, R.M.; Gertrudis, P.P.; Antonio, M. Solid-phase UV spectrophotometric method for determination of ciprofloxacin. Microchem. J. 2004, 77, 79–84. [Google Scholar] [CrossRef]
- Janusch, F.; Scherz, G.; Mohring, S. Determination of fluoroquinolones in chicken feces—A new liquid-liquid extraction method combined with LC-MS/MS. Environ. Toxicol. Pharmacol. 2014, 38, 792–799. [Google Scholar] [CrossRef]
- Javier, M.; José, J.L. New Raman-Laser-Induced Breakdown Spectroscopy Identity of Explosives Using Parametric Data Fusion on an Integrated Sensing Platform. Anal. Chem. 2011, 83, 6275–6285. [Google Scholar] [CrossRef]
- David, M.G.; Francisco, J.L.; Nikola, J.; Laura, G.G. Determination of aminoglycosides in honey by capillary electrophoresis tandem mass spectrometry and extraction with molecularly imprinted polymers. Anal. Chim. Acta 2015, 891, 321–328. [Google Scholar] [CrossRef]
- Cristina, B.; Antonio, D.C.; Yolanda, P. Determination of tetracyclines in multi-specie animal tissues by pressurized liquid extraction and liquid chromatography-tandem mass spectrometry. Food Chem. 2009, 116, 1005–1012. [Google Scholar] [CrossRef]
- Hong, C.; Li, L.; Zou, J.Y.; You, S.Y.; Wang, E.L. On–Off Ratiometric Fluorescence Europium(III) Metal-Organic Framework for Quantitative Detection of the Inflammatory Marker Neopterin. Inorg. Chem. 2024, 63, 4697–4706. [Google Scholar] [CrossRef] [PubMed]
- Wang, S.; Sun, B.; Sun, J.; Li, X.; Liu, Y.; Su, Z. Lanthanide metal organic frameworks as fluorescence sensors for temperature and antibiotics differentiation. Dyes Pigm. 2024, 223, 111930. [Google Scholar] [CrossRef]
- Xie, Y.; Sun, G.T.; Mandl, G.A.; Maurizio, S.L.; Chen, J.B. Upconversion Luminescence through Cooperative and Energy-Transfer Mechanisms in Yb3+ -Metal-Organic Frameworks. Angew. Chem. Int. Ed. 2023, 62, e202216269. [Google Scholar] [CrossRef]
- Wang, C.Y.; Wang, C.C.; Zhang, X.W.; Ren, X.Y.; Yu, B.Y.; Wang, P.; Zhao, Z.X.; Fu, H.F. A new Eu-MOF for ratiometrically fluorescent detection toward quinolone antibiotics and selective detection toward tetracycline antibiotics. Chin. Chem. Lett. 2022, 33, 1353–1357. [Google Scholar] [CrossRef]
- Yang, D.D.; Shi, Y.S.; Xiao, T.; Fang, Y.H.; Zheng, X.J. Three-Dimensional Viologen-Based Lanthanide-Organic Frameworks: Photochromism and Fluorescence Detection of Quinolone Antibiotics. Inorg. Chem. 2023, 62, 6084–6091. [Google Scholar] [CrossRef]
- Sheldrick, G.M. SADABS, Program for Empirical Absorption Correction of Area Detector Data; University of Gottingen: Gottingen, Germany, 2010. [Google Scholar]
- Dolomanov, O.V.; Bourhis, L.J.; Gildea, R.J.; Howard, J.A.K.; Puschmann, H. OLEX2: A complete structure solution, refinement and analysis program. J. Appl. Cryst. 2009, 42, 339–341. [Google Scholar] [CrossRef]
- Sheldrick, G.M. Crystal structure refinement with SHELXL. Cryst. Struct. Commun. 2015, 71, 3–8. [Google Scholar] [CrossRef]
- Zhou, J.M.; Li, H.H.; Zhang, H.; Li, H.M.; Shi, W.; Cheng, P. A bimetallic lanthanide metal- organic material as a self-calibrating color-gradient luminescent sensor. Adv. Mater. 2015, 27, 7072–7077. [Google Scholar] [CrossRef] [PubMed]
- Wang, H.; Wang, S.; Li, H.; Chen, X. Syntheses, structures and luminescent properties of Eu- and Tb-mofs with 3,5-pyridinedicarboxylate and 1,2-benzenedicarboxylate. J. Fluoresc. 2021, 31, 1393–1399. [Google Scholar] [CrossRef]
- Yang, K.R.; Jia, P.; Hou, J.J.; Bu, T.; Sun, X.Y.; Liu, Y.N.; Wang, L. Innovative Dual-Emitting Ratiometric Fluorescence Sensor for Tetracyclines Detection Based on Boron Nitride Quantum Dots and Europium Ions. ACS Sustain. Chem. Eng. 2020, 8, 17185–17193. [Google Scholar] [CrossRef]
- Sun, C.Y.; Su, R.F.; Bie, J.X.; Sun, J.H.; Qiao, S.N.; Ma, X.Y.; Sun, R.; Zhang, T.H. Label-free fluorescent sensor based on aptamer and thiazole orange for the detection of tetracycline. Dyes Pigm. 2018, 149, 867–875. [Google Scholar] [CrossRef]
- Xu, J.; Shen, X.K.; Jia, L.; Zhou, T.; Ma, T.L.; Xu, Z.Q.; Cao, J.L.; Ge, Z.J.; Bi, N.; Zhu, T.F.; et al. A novel visual ratiometric fluorescent sensing platform for highly-sensitive visual detection of tetracyclines by a lanthanide-functionalized palygorskite nanomaterial. J. Hazard. Mater. 2018, 342, 158–165. [Google Scholar] [CrossRef]
- Yin, S.N.; Tong, C.L. Lanthanide coordination polymer nanoparticles as a ratiometric fluorescence sensor for real-time and visual detection of tetracycline by a smartphone and test paper based on the analyte-triggered antenna effect and inner filter effect. Anal. Chim. Acta 2022, 1206, 339809. [Google Scholar] [CrossRef]
- Li, Y.; Min, Q.; Wang, Y.; Zhuang, X.; Hao, X.; Tian, X.; Fu, X.; Luan, F. A portable visual coffee ring based on carbon dot sensitized lanthanide complex coordination to detect bisphenol a in water. RSC Adv. 2022, 12, 7306–7312. [Google Scholar] [CrossRef]
- Zhang, Y.; Wang, A.; Feng, S.; Yuan, C.; Lu, L. Syntheses and fluorescence properties of lanthanide isostructural complexes derived from aspartic acid. Dalton Trans. 2023, 52, 5243–5251. [Google Scholar] [CrossRef] [PubMed]
- Zhang, L.; Wang, Y.; Chen, J.; Liu, W.; Zhou, P.; Yang, G.; Li, X. Molecular docking approaches for green-synthesized nanoparticle-biointeractions. Molecules 2024, 29, 2428. [Google Scholar] [CrossRef]
- Gao, Z.H.; Fu, L.S.; Dong, G.Y.; Qin, C.L. Two robust Zn-CPs as multiresponsive turn-on fluorescent sensors for the detection of five quinolone antibiotics. J. Mol. Struct. 2024, 1318, 139339. [Google Scholar] [CrossRef]
- Tang, R.J.; Li, L.F.; Zhu, Y.W.; Zhan, M.H.; Zhao, J.; Jiang, C.L.; Liu, B.H. Ratiometric fluorescent sensor for sensitive visualization of full-spectrum fluoroquinolone antibiotic residues in the environment. Microchem. J. 2025, 212, 113260. [Google Scholar] [CrossRef]
- Xie, R.; Yang, P.; Liu, J.; Zou, X.; Tan, Y.; Wang, X.; Tao, J.; Zhao, P. Lanthanide-functionalized metal-organic frameworks based ratiometric fluorescent sensor array for identification and determination of antibiotics. Talanta 2021, 231, 122366. [Google Scholar] [CrossRef]
- Chi, J.; Song, Y.Y.; Feng, L. A ratiometric fluorescence sensor with different responsive modes based on carbon dots-embedded Tb-MOFs for the determination of norfloxacin and levofloxacin. Talanta 2024, 280, 126763. [Google Scholar] [CrossRef] [PubMed]
- Sowndarya, A.; Thangadurai, T.D.; Nataraj, D. Morphology-transforming AuNPs-based fluorescent probe for ultra-low sensitive detection of levofloxacin in urine samples at pH 7.0 through excimer formation. J. Mol. Liq. 2024, 407, 125156. [Google Scholar] [CrossRef]
- Ye, Y.W.; Wu, T.T.; Jiang, X.T.; Cao, J.X.; Ling, X.; Mei, Q.S.; Chen, H.; Han, D.M.; Xu, J.-J.; Shen, Y.Z. Portable Smartphone-Based QDs for the Visual Onsite Monitoring of Fluoroquinolone Antibiotics in Actual Food and Environmental Samples. ACS Appl. Mater. Interfaces 2020, 12, 14552–14562. [Google Scholar] [CrossRef]
- Xiao, T.; Yang, D.-D.; Shi, Y.-S.; Zheng, H.-W.; Xia, Z.-G.; Zheng, X.-J. Hydrazone-Based Europium(III) Complexes: Mechanochromic Luminescenceand Turn-On Fluorescence Detection of Quinolone Antibioticsin Human Urine. Cryst. Growth Des. 2023, 23, 5957–5964. [Google Scholar] [CrossRef]
- Wang, D.H.; Kang, H.; Wang, X.R.; Zhou, W. Fluorescence turn off-on continuous response of dual lanthanide metal organic frameworks for selective detecting fluoroquinolone antibiotics. J. Solid State Chem. 2024, 333, 124635. [Google Scholar] [CrossRef]
- Yu, M.; Xie, Y.; Wang, X.; Li, Y.X.; Li, G. Highly water-stable Dye@Ln-MOFs for sensitive and selective detection toward antibiotics in water. ACS Appl. Mater. Inter. 2019, 11, 21201–21210. [Google Scholar] [CrossRef]
- Lin, J.S.; Yang, S.L.; Wang, Y.J.; Cui, Y.H.; Li, Q.Y.; Chen, Y.H.; Ding, L. Sensitive detection of levofloxacin and copper (II) based on fluorescence “turn on-off” of biomass carbonized polymer dots. J. Ind. Eng. Chem. 2022, 114, 288–296. [Google Scholar] [CrossRef]
- Guo, Y.J.; Li, L.F.; Xu, S.H.; Zhang, M.F.; Jiang, C.L. Ion coordination and chelation in Eu-MOFs matrices: Ultrafast fluorescence visual quantification monitoring of antibiotic residues. Talanta 2024, 278, 126549. [Google Scholar] [CrossRef]
- Xia, M.; Ma, W.C.; Zhao, L.N.; Liu, H.B. Highly Selective and Sensitive Detection of Quinolone Antibiotics Using Lanthanide Metal–Organic Framework- Based White- Light Materials. Luminescence 2025, 40, e70227. [Google Scholar] [CrossRef] [PubMed]
- Meng, S.; Mu, B.F.; Mao, S.; Li, Z. Dual-lanthanide functionalized hydrogen-bonded organic frameworks for fluorescent detection of quinolone antibiotics in multi-media. J. Hazard. Mater. 2025, 496, 139335. [Google Scholar] [CrossRef] [PubMed]






| Antibiotics | C (μM) | Founded (μM) | Recovery Rate (%) | RSD (%, n = 3) |
|---|---|---|---|---|
| OFX | 7.5 | 7.42 | 98.93 | 3.1 |
| 10 | 10.39 | 103.90 | 2.6 | |
| 15 | 16.01 | 106.73 | 1.2 | |
| LFX | 7.5 | 7.28 | 97.07 | 2.0 |
| 10 | 9.08 | 90.80 | 1.7 | |
| 15 | 15.73 | 104.87 | 0.9 |
| Sample | Complex 1 | Complex 1@OFX | Complex 1@LFX | Complex 1@NFX |
|---|---|---|---|---|
| QY (488 nm) | 1.82% | 22.56% | 21.58% | |
| QY (545 nm) | 5.53% | 13.82% |
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Wang, A.; Li, Y.; Zhao, W.; Liu, J. A Tb (Ⅲ) Coordination Polymer Based on 5-(2-(Pyrazole-1-yl) Pyridine-5-yl) Terephthalic Acid and Its Visual Detection of Quinolone Antibiotics. Polymers 2025, 17, 2277. https://doi.org/10.3390/polym17172277
Wang A, Li Y, Zhao W, Liu J. A Tb (Ⅲ) Coordination Polymer Based on 5-(2-(Pyrazole-1-yl) Pyridine-5-yl) Terephthalic Acid and Its Visual Detection of Quinolone Antibiotics. Polymers. 2025; 17(17):2277. https://doi.org/10.3390/polym17172277
Chicago/Turabian StyleWang, Ai, Yichong Li, Wei Zhao, and Jia Liu. 2025. "A Tb (Ⅲ) Coordination Polymer Based on 5-(2-(Pyrazole-1-yl) Pyridine-5-yl) Terephthalic Acid and Its Visual Detection of Quinolone Antibiotics" Polymers 17, no. 17: 2277. https://doi.org/10.3390/polym17172277
APA StyleWang, A., Li, Y., Zhao, W., & Liu, J. (2025). A Tb (Ⅲ) Coordination Polymer Based on 5-(2-(Pyrazole-1-yl) Pyridine-5-yl) Terephthalic Acid and Its Visual Detection of Quinolone Antibiotics. Polymers, 17(17), 2277. https://doi.org/10.3390/polym17172277
