Oxytetracycline Ratio Fluorescence Detection Based on Europium Metal-Organic Framework Encapsulated Cs3Bi2Br9 Quantum Dots

doi:10.16552/j.cnki.issn1001-1625.2025.1054

Abstract

Abstract:

The specific detection of oxytetracycline （OTC） residues is of great significance for food safety and environmental monitoring. The rapid and specific determination of OTC in the environment remains a challenge. In this study， Cs₃Bi₂Br₉ was encapsulated in an Eu-based metal-organic framework （Eu-MOF） to construct a ratio fluorescence sensor， Cs₃Bi₂Br₉@Eu-MOF， for the detection of OTC. The results show that the sensor exhibits optimal performance when anhydrous ethanol is used as the anti-solvent and the preparation is carried out under an oil bath temperature of 60 ℃ and pH=7. The sensing mechanism indicates that， with increasing OTC concentration in the range of 0~16 μmol·L^-1， the blue fluorescence emission peak intensity of Cs₃Bi₂Br₉@Eu-MOF at 424 nm gradually decreases due to the inner filter effect， while a red fluorescence emission peak at 616 nm appears and its intensity gradually increases due to the sensitization of Eu³⁺ by OTC. Based on the ratio signal （F₆₁₆/F₄₂₄）， the Cs₃Bi₂Br₉@Eu-MOF ratio fluorescence sensor demonstrates high sensitivity and a low detection limit for OTC， and excellent selectivity and anti-interference ability.

Key words: Cs₃Bi₂Br₉, Eu-MOF, oxytetracycline, ratio fluorescence, water stability, lead-free

CLC Number:

TP212

ZHENG Jiahong, GUO Kang. Oxytetracycline Ratio Fluorescence Detection Based on Europium Metal-Organic Framework Encapsulated Cs₃Bi₂Br₉ Quantum Dots[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(5): 1790-1800.

Figures/Tables 11

Fig.1 Schematic diagram of preparation process of Cs3Bi2Br9@Eu-MOF

Fig.2 XRD patterns， SEM image， TEM images and EDS surface scanning element distribution of samples

Fig.3 Adsorption-desorption isotherms and pore size distribution curves （inset） of Cs3Bi2Br9@Eu-MOF and Eu-MOF and FTIR spectrum of Cs3Bi2Br9@Eu-MOF

Fig.4 XPS spectra of Cs3Bi2Br9@Eu-MOF and Cs3Bi2Br9

Fig.5 Effects of different factors on fluorescence intensity of Cs3Bi2Br9@Eu-MOF

Fig.6 Response time of Cs3Bi2Br9@Eu-MOF to OTC and water stability of Cs3Bi2Br9@Eu-MOF

Fig.7 Fluorescence response spectra and linear relationship of Cs3Bi2Br9@Eu-MOF， Cs3Bi2Br9 and Eu-MOF to different concentrations of OTC

Table 1 Comparison of different OTC detection methods

Sensing probe	Detection range/（μmol·L^-1）	Limit of detection/（μmol·L^-1）	Ref
COF-TD@Eu³⁺	5~40	0.79	［33］
Cs₃Bi₂Br₉	2~18	0.432	［34］
CuInS₂/ZnS	0~50	0.46	［35］
Cs₃Bi₂Br₉@Eu-MOF	2~16	0.254	This work

Fig.8 Selectivity and anti-interference property of Cs3Bi2Br9@Eu-MOF ratio fluorescence probe for OTC

Fig.9 Excitation spectra and UV-vis absorption spectra of samples and fluorescence lifetime plots of Cs3Bi2Br9@Eu-MOF with and without OTC

Table 2 OTC detection rate in spiked water samples

Sample	Spkied water concentraion/（μmol·L^-1）	OTC detection concentration/（μmol·L^-1）	Recovery/%
1	5	5.06	101.20
2	10	10.09	100.94
3	15	14.62	97.46

References 37

[1]	CHEN C， WANG L L， XU L， et al. Highly sensitive oxytetracycline detection using QCM and molecularly imprinted polymers with deep eutectic solvents［J］. Polymers， 2025， 17（7）： 946.
[2]	AMANGELSIN Y， SEMENOVA Y， DADAR M， et al. The impact of tetracycline pollution on the aquatic environment and removal strategies［J］. Antibiotics， 2023， 12（3）： 440.
[3]	SEBAIY M M， HASSAN W S， ELHENNAWY M E. Developing a high-performance liquid chromatography （HPLC） method for simultaneous determination of oxytetracycline， tinidazole and esomeprazole in human plasma［J］. Journal of Chromatographic Science， 2019， 57（8）： 724-729.
[4]	MORENO-GONZÁLEZ D， KRULIŠOVÁ M， GÁMIZ-GRACIA L， et al. Determination of tetracyclines in human urine samples by capillary electrophoresis in combination with field amplified sample injection［J］. Electrophoresis， 2018， 39（4）： 608-615.
[5]	YU X Z， ZHANG X Y， WANG Z H， et al. Universal simultaneous multiplex ELISA of small molecules in milk based on dual luciferases［J］. Analytica Chimica Acta， 2018， 1001： 125-133.
[6]	BARDHI A， GAZZOTTI T， PAGLIUCA G， et al. Validation of a single liquid chromatography-tandem mass spectrometry approach for oxytetracycline determination in bull plasma， seminal plasma and urine［J］. Drug Testing and Analysis， 2022， 14（7）： 1338-1342.
[7]	YI K Y. CdTe/ZnS quantum dots as fluorescent probes for ammonium determination［J］. Luminescence， 2016， 31（4）： 952-957.
[8]	JU S M， MAO C M， ZHENG J P， et al. Perovskite quantum dot light-emitting memcapacitor［J］. ACS Applied Nano Materials， 2023， 6（11）： 9219-9225.
[9]	ARAGON A G， WIGGINS T E， MA X， et al. Lead-free Cs₃Bi₂Br₉ and Cs₃Bi_2- _x Sb _x Br₉ nanocrystals as photocatalysts with enhanced activity for the degradation of rhodamine in aqueous environments［J］. Journal of Photochemistry and Photobiology A： Chemistry， 2023， 436： 114391.
[10]	WANG N， LI H R， TIAN Y B， et al. Molecularly imprinted ratiometric fluorescence sensor for visual detection of 17β-estradiol in milk： a generalized strategy toward imprinted ratiometric fluorescence construction［J］. Mikrochimica Acta， 2024， 191（5）： 249.
[11]	LI P， ZHANG S， YANG X Y， et al. Integrating Au@MOF@COF nanocomposites for electrochemical aptasensing of trace oxytetracycline［J］. Nano Research， 2025， 18（10）： 94907590.
[12]	WEI R J， LUO X， NING G H， et al. Covalent metal-organic frameworks： fusion of covalent organic frameworks and metal-organic frameworks［J］. Accounts of Chemical Research， 2025， 58（5）： 746-761.
[13]	LIU M W， LIU G L， WANG Y F， et al. Applications of multifunctional metal-organic frameworks in perovskite photovoltaics： roles， advantages and prospects［J］. Materials Chemistry Frontiers， 2024， 8（4）： 869-879.
[14]	REN C W， LI Z P， HUANG L， et al. Confinement of all-inorganic perovskite quantum dots assembled in metal-organic frameworks for ultrafast scintillator application［J］. Nanoscale， 2022， 14（11）： 4216-4224.
[15]	CUI Y， CHEN F， YIN X B. A ratiometric fluorescence platform based on boric-acid-functional Eu-MOF for sensitive detection of H₂O₂ and glucose［J］. Biosensors and Bioelectronics， 2019， 135： 208-215.
[16]	LAI W W， WU C L， HAN X X. Facile synthesis of hyperbranched Eu-MOF structures for the construction of a CsPbBr₃/Eu-MOF composite and its application as a ratiometric fluorescent probe［J］. Journal of Materials Chemistry C， 2023， 11（8）： 2995-3002.
[17]	FANG Z H， YUE X Y， XIANG Q J. Atomically contacted Cs₃Bi₂Br₉ QDs@UiO-66 composite for photocatalytic CO₂ reduction［J］. Small， 2024， 20（34）： 2401914.
[18]	DING N， ZHOU D L， PAN G C， et al. Europium-doped lead-free Cs₃Bi₂Br₉ perovskite quantum dots and ultrasensitive Cu²⁺ detection［J］. ACS Sustainable Chemistry & Engineering， 2019， 7（9）： 8397-8404.
[19]	SHU Y， YE Q Y， DAI T， et al. Incorporation of perovskite nanocrystals into lanthanide metal-organic frameworks with enhanced stability for ratiometric and visual sensing of mercury in aqueous solution［J］. Journal of Hazardous Materials， 2022， 430： 128360.
[20]	LI C， YANG Q F， LIU D K， et al. Removal of organic phosphonate HEDP by Eu-MOF/GO composite membrane［J］. Journal of Environmental Chemical Engineering， 2021， 9（6）： 106895.
[21]	LIU J L， LI C， ZHANG S， et al. Environment-friendly lead-free Cs₃Bi₂Br₉ perovskite quantum dots as fluorescent probes for rapid detection of oxytetracycline via inner filter effect［J］. Journal of Cluster Science， 2024， 36（1）： 22.
[22]	ZHOU C， XU F F， WANG W， et al. Simple synthesis of dual-emission CsPbBr₃@EuBTC composite for latent fingerprints and optical anti-counterfeiting applications［J］. Materials Today Communications， 2022， 33： 104493.
[23]	DANG S， SONG S Y， FENG J， et al. Microwave-assisted synthesis of nanoscale Eu（BTC）（H₂O）·DMF with tunable luminescence［J］. Science China Chemistry， 2015， 58（6）： 973-978.
[24]	XU L N， LI Y N， PAN Q J， et al. Dual-mode light-emitting lanthanide metal-organic frameworks with high water and thermal stability and their application in white LEDs［J］. ACS Applied Materials & Interfaces， 2020， 12（16）： 18934-18943.
[25]	XIAO J Y， REN Y， LIU M L， et al. Ultrasensitive detection of Vibrio parahaemolyticus based on boric acid-functionalized Eu （III）-based metal： organic framework［J］. Analytica Chimica Acta， 2025， 1344： 343682.
[26]	DING L， DING Y P， BAI F H， et al. In situ growth of Cs₃Bi₂Br₉ quantum dots on Bi-MOF nanosheets via cosharing bismuth atoms for CO₂ capture and photocatalytic reduction［J］. Inorganic Chemistry， 2023， 62（5）： 2289-2303.
[27]	DING Y， WANG C H， BANDARU S， et al. Cs₃Bi₂Br₉ nanoparticles decorated C₃N₄ nanotubes composite photocatalyst for highly selective oxidation of benzylic alcohol［J］. Journal of Colloid and Interface Science， 2024， 672： 600-609.
[28]	HAI O， LI P， LI J， et al. K⁺-doped lead-free Cs₃Bi₂Br₉ nanocrystals enable efficient blue emission and ultra-stability［J］. Ceramics International， 2025， 51（4）： 5053-5060.
[29]	BAI Z J， MAO Y， WANG B H， et al. Tuning photocatalytic performance of Cs₃Bi₂Br₉ perovskite by g-C₃N₄ for C（sp³）： H bond activation［J］. Nano Research， 2023， 16（5）： 6104-6112.
[30]	LI F M， FENG Y F， HUANG Y P， et al. Colorimetric sensing of chloride in sweat based on fluorescence wavelength shift via halide exchange of CsPbBr₃ perovskite nanocrystals［J］. Microchimica Acta， 2021， 188（1）： 2.
[31]	LIU Q R， LIU B， QIU M M， et al. A Europium MOF-based turn-off fluorescent sensor for tryptophan detection in human serum， urine and lake water［J］. Journal of Solid State Chemistry， 2022， 311： 123138.
[32]	POURSAM Y， TAHMASEBI N， et al. Utilizing the water instability of Cs₃Bi₂Br₉ perovskite for in situ growth of BiOBr nanosheets on g-C₃N₄ toward enhanced photocatalytic activity［J］. ACS Applied Nano Materials， 2025， 8（13）： 6465-6478.
[33]	LONG Q H， HONG L N， HAN C， et al. Eu³⁺-functionalized covalent organic framework for ratiometric fluorescence detection and adsorption of tetracycline and information steganography［J］. Mikrochimica Acta， 2024， 191（9）： 519.
[34]	WEI X， GAO Y， ZHANG S， et al. Non-toxic Cs₃Bi₂Br₉ quantum dots molecular imprinted nanocomposite with boronate affinity and imprinting selectivity for selective detection of oxytetracycline［J］. Journal of Alloys and Compounds， 2024， 1002： 175329.
[35]	CHEN X P， LIN J W， ZHUANG Y F， et al. Dual-mode turn-on ratiometric fluorescence sensor based on carbon dots and CuInS₂/ZnS quantum dots for detection of chlorotetracycline［J］. Spectrochimica Acta Part A： Molecular and Biomolecular Spectroscopy， 2022， 270： 120851.
[36]	TAN S Y， WANG Q， TAN Q X， et al. Ratiometric fluorescence probe based on deep-red emissive CdTe quantum dots and Eu³⁺ hybrid for oxytetracycline detection［J］. Chemosensors， 2023， 11（1）： 62.
[37]	ZU F L， YAN F Y， BAI Z J， et al. The quenching of the fluorescence of carbon dots： a review on mechanisms and applications［J］. Microchimica Acta， 2017， 184（7）： 1899-1914.

Oxytetracycline Ratio Fluorescence Detection Based on Europium Metal-Organic Framework Encapsulated Cs₃Bi₂Br₉ Quantum Dots

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