Research Progress on Fluorescence Detection of Antibiotics by Metal-Organic Frameworks

doi:10.16553/j.cnki.issn1000-985x.2025.0122

Abstract

Abstract: Antibiotics， as essential antimicrobial agents， are extensively used in medicine， agriculture， and various industrial sectors. However， their overuse and improper disposal have led to environmental contamination and the accumulation of antibiotic residues in water bodies， posing significant risks to human health and ecological balance. Conventional detection techniques—such as gas chromatography （GC）， liquid chromatography （LC）， gas chromatography-mass spectrometry （GC-MS）， and liquid chromatography-mass spectrometry （LC-MS）—though highly accurate， are often impeded by high costs， operational complexity， and time-intensive procedures， rendering them unsuitable for on-site and large-scale monitoring. Thus， there is a pressing need to develop efficient and sensitive detection technologies for quantifying antibiotic levels in food and environmental samples. Metal-organic frameworks （MOFs）， characterized by their unique porous structures， tunable chemical compositions， and exceptional fluorescence properties， have shown great promise for the fluorescent detection of antibiotics. Employing a literature review approach， this paper explores the fundamental mechanisms underlying MOF-based fluorescence sensing， including photoinduced electron transfer （PET）， Förster resonance energy transfer （FRET）， and the inner filter effect （IFE）. It systematically summarizes recent advances in fluorescent sensors constructed from MOFs and their host-guest composites for antibiotic detection， leveraging three primary signal transduction strategies： fluorescence quenching， fluorescence enhancement， and ratiometric fluorescence. This review bridges the conventional divides between chemical materials science， biomedicine， and environmental science， and investigates the innovative potential of MOFs in antibiotic monitoring across medical， agricultural， and industrial contexts. Specifically， it outlines the performance of MOF-based sensors in detecting major antibiotic classes， such as β-lactams， macrolides， tetracyclines， aminoglycosides， quinolones， sulfonamides， amphenicols， and phosphoglycolipids. Through strategies such as fluorescence quenching， enhancement， and ratiometric sensing， the reviewed MOF-based sensors demonstrate excellent performance. The quenching strategy exploits interactions between antibiotics and MOFs to markedly suppress fluorescence intensity， enabling highly sensitive detection. Conversely， the enhancement strategy capitalizes on the ability of certain antibiotics to augment MOF fluorescence under specific conditions， significantly amplifying weak signals and reducing interference. Ratiometric sensing employs the ratio of fluorescence intensities at two different wavelengths as a detection parameter， thereby improving accuracy and anti-interference capacity. This approach may involve one signal increasing while the other decreases， simultaneous changes in both signals， or change in one signal with the other remaining constant. These fluorescent sensors are characterized by straightforward operation， fast response， and relatively low cost， presenting promising alternatives for addressing challenges in antibiotic residue detection. Moreover， they exhibit distinct performance characteristics across different antibiotic classes， offering versatile and effective technical pathways for antibiotic analysis. In summary， fluorescent sensors based on MOFs and their host-guest composites demonstrate broad application prospects in antibiotic detection. By synthesizing and critically evaluating existing research， this review also outlines future directions for the field， including further optimization of MOF structures and properties， refinement of synthesis methods， and the integration of advanced machine learning techniques for data processing and analysis. This work provides a foundation for promoting the practical deployment of MOF-based fluorescent sensors， thereby supporting efforts to mitigate antibiotic pollution and protect human health and environmental safety.

Key words: metal-organic framework; fluorescence detection; fluorescence sensor; antibiotic; environmental and food pollution

CLC Number:

O657.3

LI Kehua, YI Kuiyu, SHI Hongwei, KANG Xiaoqi. Research Progress on Fluorescence Detection of Antibiotics by Metal-Organic Frameworks[J]. Journal of Synthetic Crystals, 2025, 54(11): 1881-1892.

Figures/Tables 12

References 60

[1]	BASSETTI S， TSCHUDIN-SUTTER S， EGLI A， et al. Optimizing antibiotic therapies to reduce the risk of bacterial resistance［J］. European Journal of Internal Medicine， 2022， 99： 7-12.
[2]	ZENG Y B， CHANG F Q， LIU Q， et al. Recent advances and perspectives on the sources and detection of antibiotics in aquatic environments［J］. Journal of Analytical Methods in Chemistry， 2022， 2022（1）： 5091181.
[3]	SINGH H， THAKUR B， BHARDWAJ S K， et al. Nanomaterial-based fluorescent biosensors for the detection of antibiotics in foodstuffs： a review［J］. Food Chemistry， 2023， 426： 136657.
[4]	AKHTER S， BHAT M A， AHMED S， et al. Antibiotic residue contamination in the aquatic environment， sources and associated potential health risks［J］. Environmental Geochemistry and Health， 2024， 46（10）： 387.
[5]	ZHOU W J， XU L， JIANG B Y. Target-initiated autonomous synthesis of metal-ion dependent DNAzymes for label-free and amplified fluorescence detection of kanamycin in milk samples［J］. Analytica Chimica Acta， 2021， 1148： 238195.
[6]	LI B， LEI Q J， WANG F， et al. A stable cationic Cd（II） coordination network as bifunctional chemosensor with high sensitively and selectively detection of antibiotics and Cr（VI） anions in water［J］. Journal of Solid State Chemistry， 2021， 298： 122117.
[7]	PERIS-VICENTE J， PERIS-GARCÍA E， ALBIOL-CHIVA J， et al. Liquid chromatography， a valuable tool in the determination of antibiotics in biological， food and environmental samples［J］. Microchemical Journal， 2022， 177： 107309.
[8]	SUN Y M， ZHAO J L， LIANG L J. Recent development of antibiotic detection in food and environment： the combination of sensors and nanomaterials［J］. Mikrochimica Acta， 2021， 188（1）： 21.
[9]	DING Q Q， ZHANG W M， GUO Y H， et al. β-lactamase sensitive probe for rapid detection of antibiotic-resistant bacteria with gas chromatography-tandem mass spectrometry［J］. Analytical Chemistry， 2023， 95（14）： 6098-6106.
[10]	MONDAL P P， MUTHUKUMAR D， FATHIMA S K P， et al. Interpenetrated robust metal-organic framework with urea-functionality-decked pores for selective and ultrasensitive detection of antibiotics and oxo-anions［J］. Crystal Growth & Design， 2023， 23（11）： 8342-8351.
[11]	XIAO Y T， LIU S Y， GAO Y， et al. Determination of antibiotic residues in aquaculture products by liquid chromatography tandem mass spectrometry： recent trends and developments from 2010 to 2020［J］. Separations， 2022， 9（2）： 35.
[12]	LI F， LUO J W， ZHU B Q， et al. Pretreatment methods for the determination of antibiotics residues in food samples and detected by liquid chromatography coupled with mass spectrometry detectors： a review［J］. Journal of Chromatographic Science， 2022， 60（10）： 991-1003.
[13]	GUO X R， ZHOU L Y， LIU X Z， et al. Fluorescence detection platform of metal-organic frameworks for biomarkers［J］. Colloids and Surfaces B： Biointerfaces， 2023， 229： 113455.
[14]	LEI M Y， PAN X Z， LIU M Y， et al. A smartphone-assisted 2D Cd-MOF-based mixed-matrix membrane exhibiting visual and on-site quantitative sensing of antibiotics and pesticides for food safety［J］. Food Chemistry， 2025， 481： 144056.
[15]	NGUYEN T N， EBRAHIM F M， STYLIANOU K C. Photoluminescent， upconversion luminescent and nonlinear optical metal-organic frameworks： from fundamental photophysics to potential applications［J］. Coordination Chemistry Reviews， 2018， 377： 259-306.
[16]	LIN G， ZENG B， LI J， et al. A systematic review of metal organic frameworks materials for heavy metal removal： synthesis， applications and mechanism［J］. Chemical Engineering Journal， 2023， 460： 141710.
[17]	CHEN Z J， KIRLIKOVALI K O， LI P， et al. Reticular chemistry for highly porous metal-organic frameworks： the chemistry and applications［J］. Accounts of Chemical Research， 2022， 55（4）： 579-591.
[18]	SHEN Y W， TISSOT A， SERRE C. Recent progress on MOF-based optical sensors for VOC sensing［J］. Chemical Science， 2022， 13（47）： 13978-14007.
[19]	YI K Y， LI H， ZHANG X T， et al. Designed Tb（III）-functionalized MOF-808 as visible fluorescent probes for monitoring bilirubin and identifying fingerprints［J］. Inorganic Chemistry， 2021， 60（5）： 3172-3180.
[20]	SUN Y X， BAI X， LUO A P， et al. Ratiometric fluorescent sensor CQD _x @Co/Mn-MOF for rapid and sensitive detection of quinolone antibiotics［J］. Talanta， 2025， 293： 128034.
[21]	RAYAPPA M K， K S K， RATTU G， et al. Advances and effectiveness of metal-organic framework based bio/chemical sensors for rapid and ultrasensitive probing of antibiotic residues in foods［J］. Sustainable Food Technology， 2023， 1（2）： 152-184.
[22]	ZHANG Q R， ZHANG Z， XU S H， et al. Photoinduced electron transfer-triggered g-C₃N₄\rhodamine B sensing system for the ratiometric fluorescence quantitation of carbendazim［J］. Analytical Chemistry， 2023， 95（9）： 4536-4542.
[23]	WANG J X， YIN J， SHEKHAH O， et al. Energy transfer in metal-organic frameworks for fluorescence sensing［J］. ACS Applied Materials & Interfaces， 2022， 14（8）： 9970-9986.
[24]	LI W X， FU Y C， LIU T Y， et al. High-throughput fluorescence quantification method based on inner filter effect and fluorescence imaging analysis［J］. Spectrochimica Acta Part A： Molecular and Biomolecular Spectroscopy， 2024， 318： 124422.
[25]	CHENG X， HUANG S， LEI Q， et al. The exquisite integration of ESIPT， PET and AIE for constructing fluorescent probe for Hg（II） detection and poisoning［J］. Chinese Chemical Letters， 2022， 33（4）： 1861-1864.
[26]	WANG C Y， WANG C C， ZHANG X W， et al. A new Eu-MOF for ratiometrically fluorescent detection toward quinolone antibiotics and selective detection toward tetracycline antibiotics［J］. Chinese Chemical Letters， 2022， 33（3）： 1353-1357.
[27]	OUYANG Y N， WANG R， WANG X Y， et al. Ultrafast energy transfer beyond the Förster approximation in organic photovoltaic blends with non-fullerene acceptors［J］. Science Advances， 2025， 11（12）： eadr5973.
[28]	VERMA A K， NOUMANI A， YADAV A K， et al. FRET based biosensor： principle applications recent advances and challenges［J］. Diagnostics， 2023， 13（8）： 1375.
[29]	BURDOV V A， VASILEVSKIY M I. Exciton-photon interactions in semiconductor nanocrystals： radiative transitions， non-radiative processes and environment effects［J］. Applied Sciences， 2021， 11（2）： 497.
[30]	YANG G Z， LIU Y， TENG J S， et al. FRET ratiometric nanoprobes for nanoparticle monitoring［J］. Biosensors， 2021， 11（12）： 505.
[31]	YI K Y， ZHANG L. Designed Eu（III）-functionalized nanoscale MOF probe based on fluorescence resonance energy transfer for the reversible sensing of trace Malachite green［J］. Food Chemistry， 2021， 354： 129584.
[32]	何　伟，陈　博，刘金彦. 基于荧光内滤效应定量检测色氨酸和左氧氟沙星［J］. 分析试验室， 2024， 43（12）： 1741-1746.
	HE W， CHEN B， LIU J Y. Quantitative detection of tryptophan and levofloxacin based on inner-filter effect of fluorescence［J］. Chinese Journal of Analysis Laboratory， 2024， 43（12）： 1741-1746 （in Chinese）.
[33]	ZHONG C L， QIU J W， TONG Y J， et al. High selective inner filter effect based method and its application in 2， 4， 6-trinitrophenol detection［J］. Dyes and Pigments， 2022， 206： 110654.
[34]	QIU H M， YANG H， GAO X， et al. Inner filter effect-based fluorescence assays toward environmental pesticides and antibiotics［J］. Coordination Chemistry Reviews， 2023， 493： 215305.
[35]	YAZHINI C， RAFI J， CHAKRABORTY P， et al. Inner filter effect on amino-functionalized metal-organic framework for the selective detection of tetracycline［J］. Journal of Cleaner Production， 2022， 373： 133929.
[36]	CHEN X L， SHANG L， LIU L， et al. A highly sensitive and multi-responsive Tb-MOF fluorescent sensor for the detection of Pb²⁺， Cr₂O₇ ^2-， B₄O₇ ^2-， aniline， nitrobenzene and cefixime［J］. Dyes and Pigments， 2021， 196： 109809.
[37]	LI R X， WANG W J， EL-SAYED E M， et al. Ratiometric fluorescence detection of tetracycline antibiotic based on a polynuclear lanthanide metal-organic framework［J］. Sensors and Actuators B： Chemical， 2021， 330： 129314.
[38]	MENG Z W， ZHANG T， ZHANG Z R， et al. Multi-metal MOF-on-MOF metal-organic gel-based visual sensing platform for ultrasensitive detection of chlortetracycline and D-penicillamine［J］. Biosensors & Bioelectronics， 2025， 271： 117012.
[39]	TANG S F， WANG J Y， XIE H H， et al. Four three-dimensional rare earth metal-organic framework fluorescent sensor for efficient detection of gentamicin sulfate and Fe³⁺ ［J］. Spectrochimica Acta Part A： Molecular and Biomolecular Spectroscopy， 2024， 322： 124765.
[40]	CHEN M T， GAO S C， LIU R H， et al. Imprinted metal-organic framework for selective extraction and determination of fluoroquinolone antibiotics in food samples［J］. LWT， 2025， 223： 117743.
[41]	LAI Z Z， YANG X， QIN L， et al. Synthesis， dye adsorption， and fluorescence sensing of antibiotics of a zinc-based coordination polymer［J］. Journal of Solid State Chemistry， 2021， 300： 122278.
[42]	JIA X X， ZHANG W Z， ZHANG S T， et al. Two isomorphic Cd/Mn（II） MOFs based on V-shaped carboxylic acid ligands-synthesis and application in fluorescence detection of Fe³⁺， nitroaromatic explosives and sulfonamide antibiotics［J］. Journal of Solid State Chemistry， 2025， 348： 125366.
[43]	YUE X Y， WU C Y， ZHOU Z J， et al. Fluorescent sensing of ciprofloxacin and chloramphenicol in milk samples via inner filter effect and photoinduced electron transfer based on nanosized rod-shaped Eu-MOF［J］. Foods， 2022， 11（19）： 3138.
[44]	HOU L， HUANG Y L， LIN T R， et al. A FRET ratiometric fluorescence biosensor for the selective determination of pyrophosphate ion and pyrophosphatase activity based on difunctional Cu-MOF nanozyme［J］. Biosensors and Bioelectronics： X， 2022， 10： 100101.
[45]	WANG L B， WANG J J， YUE E L， et al. Water-stable Cd-MOF with fluorescent sensing of tetracycline， pyrimethanil， abamectin benzoate and construction of logic gate［J］. Spectrochimica Acta Part A， Molecular and Biomolecular Spectroscopy， 2023， 285： 121894.
[46]	CHEN J， XU F H， ZHANG Q， et al. Tetracycline antibiotics and NH₄ ⁺ detection by Zn-organic framework fluorescent probe［J］. Analyst， 2021， 146（22）： 6883-6892.
[47]	ZHAO Y Z， HAO H Y， WANG H B， et al. Antibiotic quantitative fluorescence chemical sensor based on Zn-MOF aggregation-induced emission characteristics［J］. Microchemical Journal， 2023， 190： 108626.
[48]	CONG Z Z， SONG Z F， MA Y X， et al. Highly emissive metal-organic frameworks for sensitive and selective detection of nitrofuran and quinolone antibiotics［J］. Chemistry-An Asian Journal， 2021， 16（13）： 1773-1779.
[49]	FENG X， SHANG Y P， ZHANG K， et al. In situ ligand-induced Ln-MOFs based on a chromophore moiety： white light emission and turn-on detection of trace antibiotics［J］. CrystEngComm， 2022， 24（23）： 4187-4200.
[50]	HASANI R， EHSANI A， HASSANZADAZAR H， et al. Copper metal-organic framework for selective detection of florfenicol based on fluorescence sensing in chicken meat［J］. Food Chemistry： X， 2024， 23： 101598.
[51]	HU Y Y， LIU Y， JIANG W Q， et al. Ratiometric fluorescence sensors utilizing lanthanide coordination polymers for detecting foodborne hazards： mechanisms， design strategies， applications， and future perspectives［J］. Trends in Food Science & Technology， 2025， 161： 105034.
[52]	CAI Y Y， DONG T， BIAN Z H， et al. Metal-organic frameworks based fluorescent sensing： mechanisms and detection applications［J］. Coordination Chemistry Reviews， 2025， 529： 216470.
[53]	AZEEZ K F， SALIMI A， HALLAJ R. MOF and CdTe quantum dots entrapped hydrogel film as dual-signal ratiometric fluorometric-colorimetric sensing platform for erythromycin detection： portable smartphone-assisted visual sensing in milk and water samples［J］. Food Chemistry， 2025， 482： 143972.
[54]	LI Y， WANG Y， DU P Y， et al. Fabrication of carbon dots@hierarchical mesoporous ZIF-8 for simultaneous ratiometric fluorescence detection and removal of tetracycline antibiotics［J］. Sensors and Actuators B： Chemical， 2022， 358： 131526.
[55]	LI J Y， DAI Y X， CUI J R， et al. Dye-encapsulated Zr-based MOFs composites as a sensitive platform for ratiometric luminescent sensing of antibiotics in water［J］. Talanta， 2023， 251： 123817.
[56]	YUE X Y， FU L， LI Y， et al. Lanthanide bimetallic MOF-based fluorescent sensor for sensitive and visual detection of sulfamerazine and malachite［J］. Food Chemistry， 2023， 410： 135390.
[57]	MA J Z， SHI Y， SONG Q， et al. Efficient porphyrin integrated UiO-66 probes for ratiometric fluorescence sensing of antibiotic residues in milk［J］. Mikrochimica Acta， 2024， 191（6）： 304.
[58]	CHEN L T， LI Z J， DOU Y M， et al. Ratiometric fluoroprobe based on Eu-MOF@Tb³⁺ for detecting tetracycline hydrochloride in freshwater fish and its application in rapid visual detection［J］. Journal of Hazardous Materials， 2024， 469： 134045.
[59]	DENG T T， HE H B， CHEN H N， et al. Dual-ligand lanthanide metal-organic framework based ratiometric fluorescent platform for visual monitoring of aminoglycoside residues in food samples［J］. Talanta， 2024， 276： 126200.
[60]	GUO Y J， LI L F， ZHANG M F， et al. A self-assembly MOF-on-MOF heterostructure-driven fluorescence sensor for aerogel-based visualization detection of flavomycin［J］. Small， 2025， 21（11）： 2410911.

Synthetic substance	MOF type	Objective	Linear range	LOD	Sample	Reference
Tb-MOF	Pure MOF	CEF	0~40 µmol/L	0.179 µmol/L	Water	［36］
FCZE	Composite MOF	CTC	0.5~200 nmol/L	0.43 nmol/L	—	［38］
［Eu（L）_1/2H₂O］ _n	Pure MOF	GM	0~140 µmol/L	0.009 1 nmol/L	—	［39］
｛Zn（bib）·（SO₄）·（H₂O）｝ _n	Pure MOF	NOR	0~10 µmol/L	7.04 µmol/L	Water	［41］
［Cd₄（MTPTC）₂（DMF）₄］·5DMF·2H₂O	Pure MOF	SDZ	0~40 µmol/L	0.070 µmol/L	—	［42］
Eu-MOF	Pure MOF	CHL	5~150 µmol/L	3.16 µmol/L	Milk	［43］

Synthetic substance	MOF type	Objective	Linear range	LOD	Sample	Reference
Tb-MOF	Pure MOF	CEF	0~40 µmol/L	0.179 µmol/L	Water	［36］
FCZE	Composite MOF	CTC	0.5~200 nmol/L	0.43 nmol/L	—	［38］
［Eu（L）_1/2H₂O］ _n	Pure MOF	GM	0~140 µmol/L	0.009 1 nmol/L	—	［39］
｛Zn（bib）·（SO₄）·（H₂O）｝ _n	Pure MOF	NOR	0~10 µmol/L	7.04 µmol/L	Water	［41］
［Cd₄（MTPTC）₂（DMF）₄］·5DMF·2H₂O	Pure MOF	SDZ	0~40 µmol/L	0.070 µmol/L	—	［42］
Eu-MOF	Pure MOF	CHL	5~150 µmol/L	3.16 µmol/L	Milk	［43］

Synthetic substance	MOF type	Objective	Linear range	LOD	Sample	Reference
Cd-MOF［Cd（L）_0.5（1，2-bimb）］	Pure MOF	AMB	0~200 µmol/L	2.39 µmol/L	—	［45］
Zn-MOF	Composite MOF	OTC	0.02~13 µmol/L	0.017 nmol/L	Water	［46］
Zn-TCPE	Composite MOF	TOB	79.3~10 000 nmol/L	23.8 nmol/L	River water	［47］
Cd-MOF	Pure MOF	ENR	0~45 µmol/L	0.025 µmol/L	Water	［48］
［Ln₂（tcptp）（btca）（H₂O） _m ］ _n， Ln=Tb³⁺	Pure MOF	LVX	0~20 µmol/L	0.256 mg/kg	—	［49］
Cu-MOF	Pure MOF	FFC	1~50 µmol/L	2.93 µmol/L	Chicken	［50］

Synthetic substance	MOF type	Objective	Linear range	LOD	Sample	Reference
Cd-MOF［Cd（L）_0.5（1，2-bimb）］	Pure MOF	AMB	0~200 µmol/L	2.39 µmol/L	—	［45］
Zn-MOF	Composite MOF	OTC	0.02~13 µmol/L	0.017 nmol/L	Water	［46］
Zn-TCPE	Composite MOF	TOB	79.3~10 000 nmol/L	23.8 nmol/L	River water	［47］
Cd-MOF	Pure MOF	ENR	0~45 µmol/L	0.025 µmol/L	Water	［48］
［Ln₂（tcptp）（btca）（H₂O） _m ］ _n， Ln=Tb³⁺	Pure MOF	LVX	0~20 µmol/L	0.256 mg/kg	—	［49］
Cu-MOF	Pure MOF	FFC	1~50 µmol/L	2.93 µmol/L	Chicken	［50］

Synthetic substance	MOF type	Objective	Linear range	LOD	Sample	Reference
QDs@Al-MOF	Composite MOF	ERY	液态24.83~242.6 nmol/L；水凝胶膜26~728 pmol/L	液态2.16 nmol/L；水凝胶膜2.42 pmol/L	—	［53］
CDs@HZIF-8	Composite MOF	TC； OTC； DOX	0.5~50 µmol/L； 0.5~40 µmol/L； 0.5~40 µmol/L	6.56 nmol/L； 29.46 nmol/L； 30.58 nmol/L	Milk	［54］
FS@UIO66	Composite MOF	LEV	79.3~10 000 nmol/L	0.280 8 µmol/L	Water	［55］
Tb_0.6Eu_0.4-MOF	Pure MOF	SMZ	2~140 µmol/L	0.1 µmol/L	Fish	［56］
TCPP@UiO-66-NDC	Composite MOF	AMX	10~1 000 nmol/L； 1~100 µmol/L	27 nmol/L	Capsules； Milk	［57］
Eu-BDC	Composite MOF	TCH	0.38~75 µmol/L	0.115 µmol/L	Carp； Clam	［58］
Eu-MOF	Composite MOF	AP； AMK； KAN	0.001~100 µmol/L	0.33 nmol/L； 0.32 nmol/L； 0.30 nmol/L	Milk； Honey	［59］
NH₂-MIL-101（Eu）@Fe-MOF	Composite MOF	FLA	6~8 µmol/L	4.8 nmol/L	—	［60］