Food Chemistry: X 23 (2024) 101598

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Food Chemistry: X
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Copper metal-organic framework for selective detection of florfenicol based

on fluorescence sensing in chicken meat
Roshanak Hasani a , Ali Ehsani b , Hassan Hassanzadazar a, * , Majid Aminzare a ,
Arezou Khezerlou b
a
Department of Food Safety and Hygiene, School of Public Health, Zanjan University of Medical Sciences, Zanjan, Iran
b
Department of Food Science and Technology, Faculty of Nutrition and Food Sciences, Tabriz University of Medical Sciences, Tabriz, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: Using a hydrothermal technique, a highly sensitive metal-organic Cu-MOFs sensor has been created to detect
Cu-metal-organic frameworks florfenicol (FFC) fluorescent in chicken meat. The sensor has demonstrated the ability to respond to the presence
Florfenicol of FFC in an aqueous solution with accuracy and selectivity, as evidenced by an increase in fluorescence in­
Fluorescence
tensity. The interactions and adsorption mechanism based on hydrogen bonding, π- π, and n-π interactions
Chicken meat
demonstrate the high sensitivity and specificity of Cu-MOFs towards. FFC was detected quantitatively with a
recovery of 96.48–98.79% in chicken meat samples. Within a broad linear range of 1–50 μM, the Cu-MOFs
nanosensor exhibits a fast response time of 1 min, a low limit of detection (LOD) of 2.93 μM, and a limit of
quantification (LOQ) of 8.80 μM. The potential applicability of the Cu-MOFs nanosensor for the detection of FFC
in food matrices is confirmed by the results obtained with high-performance liquid chromatography (HPLC).
Chemical compounds: Copper (II) nitrate (PubChem CID: 18616); Terephthalic acid (PubChem CID: 7489);
Polyvinyl pyrrolidone (PubChem CID: 486422059); N, N-dimethylformamide (PubChem CID: 6228); Ethyl
alcohol (PubChem CID: 702); Hydrochloric acid (PubChem CID: 313); Sodium hydroxide (PubChem CID: 14798);
Acetic acid (PubChem CID: 176); Trichloroacetic acid (PubChem CID: 6421); Florfenicol (PubChem CID:
114811).

1. Introduction chromatography-tandem mass spectrometry (LC-MS/MS) and gas

chromatography-tandem mass spectrometry (GC–MS), ion mobility
Antibiotics are one of the utmost important medical discoveries of spectrometry, Raman spectroscopy as well as ELISA and antibiogram
the 20th century (Hutchings, Truman, & Wilkinson, 2019). The (Alizadeh Sani et al., 2023; Marimuthu, Arumugam, Sabarinathan, Li, &
improper use of antibiotics as antipathogenic and growth promotion Chen, 2021; Wang et al., 2019; Yue, Wu, Zhou, Fu, & Bai, 2022). These
agent related to animal husbandry components can cause catastrophic techniques are expensive technologies with high diagnostic costs,
contamination and accumulation of their residues in animal-derived moderate sensitivity, accuracy and reliability. Their operation is
food, water and soil resources. These residues can cause complica­ complicated and difficult and requires skilled operators and takes time
tions, including antibiotic resistance, allergic reactions, mutagenesis, (Cao et al., 2023). Hence, it is crucial to develop a new detection method
aplastic anemia and visual impairment, carcinogenesis intestinal flora that can detect antibiotics in animal foods quickly and easily (Mar­
disorders and immunopathological disorders posing a threat to human imuthu et al., 2021).
health (Xie et al., 2021). Hence, to detect antibiotic residues, estab­ Recently, sensors have comprehensive features that make them
lishment of selective, efficient, rapid and sensitive techniques is applicable in medicine, biomedicine, toxicology and environmental
important and necessary. toxicology, engineering, technology and food safety monitoring. The
Currently, a number of techniques have been reported for the design and choice of material sensing used in the sensor must consider
detection of antibiotic residues, including high performance liquid cost, stability, sensitivity, and selectivity as the main attributes (Khe­
chromatography (HPLC), gas chromatography (GC), liquid zerlou, Tavassoli, Khalilzadeh, Ehsani, & Kazemian, 2023; Mansouri

* Corresponding author.
E-mail address: [email protected] (H. Hassanzadazar).

https://doi.org/10.1016/j.fochx.2024.101598
Received 21 January 2024; Received in revised form 13 June 2024; Accepted 24 June 2024
Available online 27 June 2024
2590-1575/© 2024 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-
nc/4.0/).
R. Hasani et al. Food Chemistry: X 23 (2024) 101598

et al., 2020). Fluorescence probes get much attention among the optical completely covered with foil. In order to completely dissolve of the
sensors for detection antibiotics in water and food (Li et al., 2020). particles, the solution was placed and stirred on a magnetic stirrer at a
MOFs are composed of polymers that have two parts: metal nuclei temperature of 40 ◦ C for 1 h. Then, the flask was placed in a Teflon-lined
(metal clusters or ions) and monodentate or polydentate organic ligands hydrothermal autoclave (250 mL) and heated at a temperature of 120 ◦ C
that function as bridging molecules (Ali & Omer, 2022; Ameen, for 16 h. The solution was transferred to 50 mL tubes and centrifuged
Mohammed, & Omer, 2023; Khezerlou, Tavassoli, Khalilzadeh, et al., (4000 rpm, 5 min) after cooling at room temperature. The precipitate
2023). Commonly, lanthanides such as Zn, Al, Fe, Zr, Tb, Eu are used was washed with absolute ethanol three times. The remained blue pre­
metals as nodes of MOF-based sensors and the organic ligands of them cipitate (final product) poured onto Whatman paper and dried overnight
are carboxylates, phosphates, sulfonates, azolates,and polyamines in a vacuum oven at 50 ◦ C.
(Ahmadi et al., 2021; Jie et al., 2023; Yue et al., 2022). Metal organic
frameworks (MOFs) materials as a promising new type of crystalline 2.3. Characterization of cu-MOFs
material are widely used in research fields such as detection of antibi­
otics, drug delivery, and other chemical sensing due to structural vari­ The morphology of the obtained Cu-MOFs was investigated using a
ability, controllable adsorption and synthesis sites in gas storage field emission scanning electron microscope (FESEM) (Tescan, Czech
(Marimuthu et al., 2021; Yue et al., 2022). The interesting features of Republic). The resolution of this device was up to 1 nm and it had a
MOFs in chemical sensing, such as high porosity, high sensitivity and magnification power of up to 1 million times at a voltage of 30 kV. Also,
selectivity, rapid response, narrow fluorescence emission, structural and Energy Dispersive X-ray Spectroscopy (EDS) was used to determine the
chemical stability, lower detection limits (micro, nano, pico, pheno­ type and quantity of elements on the surface of nanomaterials collected
molar limits) and unlimited stability and surface modification has from (MIRA3 FEG-SEM) (Tescan, Czech Republic) equipped with energy
attracted great interests to applicate of them as sensors (Ahmadi et al., dispersive X-ray (EDX). An X-diffractionometer (Tong Da TD-3700,
2021; Ahmadijokani et al., 2022; Ameen et al., 2024; Mohammed China) was utilized to determine X-ray powder diffraction (XRD) and
Ameen, Qasim, Alhasan, Hama Aziz, & Omer, 2023; Yue et al., 2022). assess the crystallization and stability of the entire Cu-MOFs. The
Fluorescent sensor based on Cu-MOFs is proposed for the detection of analysis accuracy of the device is 0.02 degrees in 0.5 s, and the voltage
antibiotics in foods due to its potential for rapid detection, easy instal­ and current consumption are 30 kV and 20 mA, respectively. FT-IR
lation, low cost and optimal stability of markers. spectra were taken between 500 and 3500 cm− 1 on a Nicolet Fourier
Several studies have been conducted on the use of MOFs for the re­ spectrophotometer (TENSOR 27, BRUKER, Germany), using a KBr
covery of antibiotics such as sulfonamides, ciprofloxacin, chloram­ beamsplitter. Thermogravimetric analysis (TGA) was performed using a
phenicol, and tetracycline from different food materials (Khezerlou, (STA PT-1000 Linseis, Germany), with a heating rate of 10 ◦ C min− 1. he
Tavassoli, Khalilzadeh, et al., 2023; Xia et al., 2020; Yue et al., 2022). Brunauer-Emmett-Teller (BET) technique was used to evaluate the
Florfenicol (FFC) is a wonderful medicine belonged to amfenicol family specific surface area. The Belsorp model (MicrotracBel Corp, Japan) was
in veterinary medicine versus infections caused by gram-positive and utilized to obtain adsorption and desorption isotherms. Fluorescence
gram-negative bacteria which is used as an antibacterial agent for spectra were obtained using a JASCO spectrometer (model FP-750,
therapeutic objectives in livestock, poultry and aquaculture, instead of Japan) with the following experimental conditions: The optical
chloramphenicol (Sadeghi, Mohsenzadeh, Abnous, Taghdisi, & Rame­ voltage was 700 V, the emission and excitation split widths were both
zani, 2018). It is available as an antibiotic at a reasonable price, and its' 10 nm, and the scanning speed was 8000 nm/min. A UV–Vis spec­
quick detection in chicken meat will increase food safety in the con­ trometer (Shimadzu 2550, Japan) was used to obtain the absorption
sumption of this product. This is a great advantage for designing a MOF spectrum of the samples. A high-performance liquid chromatography
sensor to detect this antibiotic. So far there is no report for the detection device (KNAUER, Germany) was used to perform HPLC measurements
of the FFC antibiotic in chicken meat using Cu-MOFs. In this study, we (Amiripour, Ghasemi, & Azizi, 2021; Liu et al., 2019).
investigated the detection potential of FFC antibiotic in chicken meat
using Cu-MOFs sensor probe as a fluorescence platform for the first time, 2.4. Optimization of experimental conditions
and the fluorescence emission of Cu-MOFs, the recovery rate, accuracy
and sensitivity of this sensor through the addition of FFC was evaluated. Analyte identification can be made more effective through the use of
different parameters. Compositional parameters such as pH, solvent,
2. Materials and methods molar ratio of raw materials and concentration of MOFs used, as well as
process parameters such as temperature, pressure and time, and finally
2.1. Materials the interaction between the analyte and MOF. These parameters can
vary depending on how the sensor is synthesized and designed (See­
Copper (II) nitrate (Cu(NO3)2), terephthalic acid C6H4(CO2H)2 tharaj, Vandana, Arya, & Mathew, 2019).
(TPA), polyvinyl pyrrolidone (PVP), N, N-dimethylformamide (DMF), Time and pH can also affect the performance of the probe (Amiripour
Pure ethyl alcohol and Tris buffer, hydrochloric acid, sodium hydroxide, et al., 2021). The effect of time on MOF is discussed in the article. The pH
acetic acid, trichloroacetic acid were purchased from Merck (Darmstadt, response of fluorescent MOFs is a result of their coordinated organic
Germany). Acetonitrile (chromatography grade), tetracycline (TET), bonds. In cases where organic compounds are fluorescent, their pro­
chloramphenicol (CHL), florfenicol (FFC), enrofloxacin (ENR), eryth­ tonation (or deprotonation) can directly affect their fluorescence in­
romycin (ERY), penicillin (PEN), neomycin (NEO), have been purchased tensity (Shamsipur, Barati, & Nematifar, 2019). Therefore, pH plays an
from Hirkani Sanat Company (Tehran, Iran). and chicken meat was essential role in MOFs. Therefore, the pH solution was made using 0.5%
obtained from local market of Tabriz (East Azerbaijan, Iran). acetic acid, Tris buffer, and sodium hydroxide, then the pH was adjusted
to 11–3, and each pH was applied with a volume of 100 μL with three
2.2. Synthesis of cu-MOFs repetitions in the spectrofluorometer (JASCO, FP-750, Japan).

The Cu-MOFs has been prepared based on described method by 2.5. Fluorescence detection of FFC
(Huo, Li, Fan, & Pu, 2020), with some modification. First, in an Erlen­
meyer flask, 2 g of PVP were dissolved in a solution containing 12 mL of All fluorescence recognition studies of Cu-MOF were performed
DMF and 12 mL of ethanol. Then, 0.332 g of TPA and 0.724 g of Cu based on the method described by Huo et al., 2020 with some modifi­
(NO3)2 were added to this solution. A blue colored solution was cation. In a typical test procedure, different concentrations of FFC
observed and due to the light sensitivity of the resulting solution, it was standard solution (10, 25 and 50 μM) were added to separate tubes and

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Fig. 1. (A) SEM image of Cu-MOFs, (B) EDS elemental analysis of Cu-MOFs, (C) XRD patterns of Cu-MOFs, (D) FT-IR spectra of Cu-MOFs.

then diluted with Tris buffer (pH = 8.0) to 2 mL and incubated at room at 3000 rpm and the supernatant was filtered through a 0.22 μM
temperature for 30 s. Each mixture was then added to a quartz cuvette membrane filter. Then 500 μL of the Cu-MOFs solution and 500 μL of the
(10 × 10 mm), and the fluorescence intensity of the solutions was sample solution were filtered and combined with FFC standard solution
measured from 400 to 530 nm upon excitation at 380 nm. TET, CHL, (10, 25 and 50 μM) and diluted to a volume of 2 mL with Tris buffer (pH
ERY, PEN, ENR and NEO antibiotics were mixed in equal concentrations = 8). A spectrofluorometer (FP-750, JASCO, Japan) was used to calcu­
(100 μL) with 500 μL of Cu-MOFs solution and volume to 1400 μL with late the FFC concentrations in the chicken meet samples according to the
Tris buffer (pH = 8.0) to measure the selectivity of the Cu-MOFs probe to fluorescence spectrum. The efficacy of the present method was evalu­
FFC. All samples were run in triplicate for FFC measurement for statis­ ated in the specified samples by calculating the limit of detection (LOD),
tical purposes. limit of quantification (LOQ) and recovery percentage. Additionally, the
outcomes of the MOF sensor were compared with HPLC results. HPLC
analysis of antibiotic FFC was performed under the following conditions:
2.6. Fluorescence assay of FFC in chicken meat
reverse-phase HPLC column M05CLA25 (Kromasil, Nouryon, Sweden)
100–5-C18 series, (250 mm, 4.6 mm, 5 μm), column temperature 25 ◦ C
First, to remove lipids, proteins and other organic compounds, 5 g of
detector Ultraviolet wavelength was 304 nm, mobile phase consisted of
the meat sample (Spiked with different concentrations of standard FFC
water/acetonitrile with volume ratio (65,35 v/v) and flow rate was 1.0
solution (10, 25 and 50 μM)) were mixed in a solution containing 35 mL
mL/min and injection volume was 100 μL. To evaluate the application, a
of trichloroacetic acid 7.5% and 10 mL of chloroform and homogenized
standard method of addition to meat samples was performed (Alizadeh
for 5 min using a vortex. After that the samples were subjected to son­
Sani et al., 2023; Khezerlou et al., 2023).
ication for 30 min. The homogenized mixture was centrifuged for 2 min

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Fig. 2. (A) The TGA curve of Cu-MOFs, (B) The result of the BET chart, (C) Fluorescence stableness of the Cu-MOFs, (D) The effect of PH on the fluorescence
performance of Cu-MOFs.

2.7. Statistical analysis for isolation and purification, MNCs are prone to aggregation because of
their low stability. MOFs are currently the most widely investigated
All experiments were performed in three replicates and the results fluorescent material for chemical sensing, thanks to their attractive
are presented as Mean ± standard deviation, and. The statistical analysis spectral properties, infinite stability, excellent thermal stability, pore
of the obtained results was done using Excel software Microsoft 2016 capability, and external surface modification. These properties make
and the drawing of spectrum diagrams was conducted using the Origin them highly effective in detecting various targets such as metal ions,
Pro 2022 software (V9.9.0.225 (SR1)) (EA, USA). small molecules, gases, biomarkers, pH values, and temperature. The
fluorescent properties of MOFs are strongly influenced by the crystal
3. Results structures and coordination environment of the metal centers, as well as
their interactions with guest species (e.g., coordination and hydrogen
3.1. Characterization bonds, π–π interactions). This provides a solid rationale for their use in
fluorescent sensing. At present, MOFs are synthesized mainly in organic
Antibiotic detection has shown significant promise for fluorescent solvents to preserve their topological structure (Li et al., 2020).
nanomaterials, including metal nanoclusters (MNC), carbon .s (CD), Cu-MOFs were made by hydrothermally combining Cu2+ as the
quantum .s (QDs), and fluorescent metal-organic frameworks (FMOFs). metal ion node, TPA as a ligand, and PVP as an adhesive and complex
All materials, however, have intrinsic shortcomings that prevent their agent. This synthesis was performed using a reliable source and making
widespread application. For example, the presence of heavy metals in some changes. According to the mentioned reference, we have used
conventional QDs can be a threat to food safety. While CDs are too small copper nitrate instead of amino-functionalized copper as the central core

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R. Hasani et al. Food Chemistry: X 23 (2024) 101598

Fig. 3. (A) 0 to 10 min time interval stability for Cu-MOFs fluorescence intensity, (B) Fluorescence increase of Cu-MOFs compared to different types of antibiotics
(100 μL),(C) Fluorescence spectra intensity of Cu-MOFs addition several concentrations of FFC (0–50 μM), (D) Standard curve of Cu-MOFs with different concen­
trations for FFC detection.

and terephthalic acid instead of aminoterephthalic acid as a ligand, as a symmetric stretching vibration of the carboxyl category, and the distinct
result, modification has occurred in the synthesis (Huo et al., 2020). peak located at 1571.77 cm− 1 can be attributed to the asymmetric
As shown in Fig. 1A, the morphology of Cu-MOFs was investigated stretching vibration of the carboxyl group. Also, the Cu–O bond was
using SEM. The synthesized material has a nanostructure with a particle visible at 467.39 cm− 1, indicating their coordination with the carboxyl
size of 2.23 ± 0.2 μМ. Cu-MOFs' elemental composition was examined group, further demonstrating the success of the synthesis of Cu-MOFs.
using EDS to display their chemical composition, as seen in Fig. 1B. Cu- These findings are also in line with the results reported by Huo et al.
MOFs' crystal structure was examined using XRD. Fig. 1C, showed that (2020), based on the similarity of symmetric and asymmetric stretching
8.82, 14.42, 15.42, 17.72, 29.06, 31.64, 33.74, and 36.14 degrees are vibrations of the carboxyl group (Huo et al., 2020). Using TGA, the
consistent with the simulated single crystal XRD results reported by Huo thermal stability of Cu-MOFs was investigated at temperatures between
et al. (2020), which included peaks at 9.28, 17.84, 24.7, 33.02 degrees 30 and 600 ◦ C and a heating rate of 10 km in air. As shown in Fig. 2A,
(Huo et al., 2020). 16.54% weight loss is caused by solvent evaporation in pores at lower
These outcomes demonstrate that the success of the synthesis of Cu- temperatures (between 50 and 310 ◦ C). Cu-MOFs exhibited thermal
MOFs. Moreover, FT-IR was used to characterize the Cu-MOFs (Fig. 1D) stability up to 320 ◦ C, at which point they started to decompose. The
in order to disclose their functional groups and molecular structures. results of TGA analysis reported by Huo et al. (2020) on NH2-Cu-MOFs
(Fig. 1D). The symmetric and asymmetric carboxylate stretching vi­ revealed that, although they were thermally stable up to 240 ◦ C, but a
brations, which show the carboxylate groups' final coordination state, weight loss of more than 44.1% occurred. Considering the weight
are responsible for the peaks at 3604.55 and 3438.88 cm− 1. The reduction (16.54%) of our synthesized materials (Cu-MOFs) compared
distinguished peak located at 1390.58 cm− 1 can be attributed to the to the weight reduction of NH2-Cu-MOFs, it can be concluded that our

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Fig. 4. (A) Excitation (Ex) and emission (Em) spectra of FFC, (B) UV–Vis absorption spectrum of FFC (red line) and fluorescence emission spectrum of Cu-MOFs (blue
line). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

designed Cu-MOFs have superior thermal stability. Based on charac­ stacking), FFC can bind to the ligand terephthalic acid (PTA), which has
terization results, Cu-MOFs exhibit good thermic stability. The presence the chemical formula C8H6O4. On the other hand, when FFC binds to
of mesoporous material is confirmed by the adsorption and desorption Cu+ ion through their interaction, the Cu-MOF sensing platform's fluo­
isotherms, and the specific surface area value obtained from the BET rescence intensity increases. This is because the Cu-MOF structure
diagram showed 5.2052 m2/g (Fig. 2B). Given this, Wang, Xie, et al. contains numerous chemical bonds of main functional groups, including
(2019) confirmed the presence of microporous and mesoporous in this O–H bonds and CO bonds of carboxyl groups, among others. Conse­
structure and reported the specific surface area as 9.81 m2/g (Wang, Ye, quently, interactions such as n–π and π–π interactions, as well as
An, Wang, & Li, 2019). The synthesis of Cu-MOF using various tech­ hydrogen interactions between Cu-MOF and functional groups of FFC
niques and substances is the reason for the difference in the value of the (such as OH, NH of amide, etc.), may be crucial in enhancing the
specific surface between our study and Wang, Ye, et al. (2019). adsorption of FFC to MOFs. Interestingly, our designed sensor exhibits
the same response to other antibiotics; and no discernible variations in
3.2. Time stability fluorescence intensity were noticed (Fig. 3B). (van Tran et al., 2020).
Fig. 3C displays the fluorescence spectra of Cu-MOFs at various con­
The effects of pH and incubation time on fluorescence intensity were centrations. In terms of (F0–F)/F0, the fluorescence intensity of Cu-
examined in order to maximize sensitivity. As shown in Fig. 2C, the MOFs increased with FFC concentration in the range of 0 to 50 μM
fluorescence emission remained mostly unchanged from day 0 to day 30, which were reported using the calibration equation, (y = 0.0091× +
and the structure of Cu-MOFs showed good temporal stability and the 1.3505), at the coefficient of determination (R2 = 0.9904) (Fig. 3D).
storage stability of Cu-MOFs both demonstrated good temporal stability Based on computations, 2.93 μM is the limit of detection (LOD) for (n =
over a period of 30 days. 7) FFC. For FFC detection, this method has a lower LOD than traditional
fluorescent probes, indicating the higher sensitivity of Cu-MOFs.
3.3. Florfenicol sensing based on cu-MOFs Compared to the results of the study conducted by Sadeghi, Jahani,
and Belador (2016) on a designed aptasensor based on ZnS composite
Respond time and pH play a significant role in FFC recognition. By with manganese to detect FFC in meat, a higher LOD value of 24 μM was
measuring the fluorescence intensity at variable pH = 3–11, the impact obtained than in the Cu-MOFs sensor (Sadeghi et al., 2016). The com­
of pH on Cu-MOFs' ability to function as fluorescent materials was parison of our method with other antibiotic detection methods using
further explored. As depicted in Fig. 2D. In fact, the fluorescence in­ different designed MOFs is shown in the Table 2.
tensity of Cu-MOFs rises in the pH range of 3–8 and falls in the pH range
of 9–11. It was discovered as a result that pH = 8 is perfect for this 3.4. Mechanism of FFC detection
structure. Furthermore, in Fig. 3A, it was demonstrated that the fluo­
rescence intensity of Cu-MOF did not change noticeably for the reaction The mechanism of fluorescence quenching includes both static and
time assay between 0 and 10 min. Cu-MOFs have the potential to serve dynamic quenching. Three methods can be used to quench fluorescence:
as a “high-speed” fluorescent probe in FFC reconnaissance, as evidenced inner filter effect (Chou & Dennis, 2015), photo-induced electron
by the high response time observed in the first min (all measurements transfer (PET), and Förster resonance energy transfer (FRET). IFE and
and fluorescence assays were carried out at room temperature (25 ◦ C)). FRET are common among them. Resonant energy transfer (FRET) is the
A measurement of FFC's fluorescence spectrum revealed that it had two non-radiative process in which an excited donor molecule uses a dipole-
peaks: an emission peak at 281 nm and an excitation peak at 228 nm dipole interaction to transfer energy to a ground state acceptor molecule
(Fig. 4A). The analyses demonstrate that the addition of FFC signifi­ (Chou & Dennis, 2015; Kaur, Kaur, & Ahuja, 2020). The efficiency of
cantly boosts Cu-MOFs' fluorescence; in fact, the porous structure of energy transfer is dependent on the degree of spectral overlap between
MOFs permits the analyte to enter the MOFs' space selectively and the acceptor and donor emission spectra as well as the relative positions
manifest as a fluorescence peak. By means of the accumulation of Pi (π–π of the two dipoles (Feng et al., 2021). On the other hand, when FRET

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Fig. 5. A schematic diagram of the Cu-MOF achieving selective fluorescence detection of florfenicol in chicken.

3.5. Detection of FFC s in chicken meat

Table 1
Comarison the accuracy and reproducibility of Cu-MOFs sensor with HPLC
The Cu-MOFs sensor was utilized to measure the FFC concentration
method to detect of spiked concentrations of florefenicol in chicken meat.
in order to examine the use of the nanosensor in a real sample of chicken
Spiked Founded of Cu- Founded of HPLC Recoveries RSD(n meat (Fig. 5). As demonstrated in Table 1, the recovery rate acquired
(μM) MOFs (μM) (μM) (%) = 3)
ranged from 96.48% to 98.79% at different concentrations (10, 25 and
10 9.83 ± 0.012 7.45 ± 0.347 98.35 0.53 50 μM), with corresponding relative standard deviation (RSD, n = 3) of
25 24.12 ± 0.016 22.22 ± 0.673 96.48 0.62
0.53 and 0.62%, respectively. The LOD and LOQ for this work were 2.93
50 49.39 ± 0.047 48.60 ± 0.062 98.79 0.16
μM and 8.80 μM, respectively. The analytical results indicate the com­
plex components in chicken samples did not cause considerable inter­
takes place, the organic ligand's (the energy donor's) fluorescence typi­ ference on the sensing potency of the Cu-MOFs. Furthermore, the results
cally decreases rather than increases. On the other hand, the overlap were in agreement with the HPLC results, suggesting that the Cu-MOF
between the analyte's absorption spectrum and its emission excitation probe can be reliable for the detection of FFC in actual samples due to
spectrum is what causes the IFE process (Al-Hashimi, Omer, & Rahman, its appropriate reproducibility and acceptable accuracy (Table 1).
2020). Measurements were made of the antibiotic's UV–Vis spectrum This study explores fluorescence detection of FFC in chicken meat
and the Cu-MOFs' excitation spectrum to validate the absorption by using Cu metal-organic framework (MOF) materials. So far, Cu-MOFs
UV–Vis and to support such a mechanism, as illustrated in Fig. 4B shows have not been used for the detection of FFC. Florfenicol is available as
a good overlap between the FFC absorption spectrum and the Cu-MOFs an antibiotic at a reasonable price, and its quick detection in chicken
excitation spectrum. This suggests that because of the high selectivity of meat will increase food safety in the consumption of this product.
Cu-MOFs, IFE, which can effectively block the excitation light for Cu- Chicken meat is a complex food item that Cu-MOFs show the ability to
MOFs and alter the energy transfer from organic ligands to Cu2+ ions detect in this research. In this study, we have precipitated and removed
and the fluorescence spectrum, may be useful for the detection of FFC. disturbing and soothing factors such as lipids and proteins as much as
The FFC display exhibits a visible UV absorption peak at 304 nm (red possible as a practical method that is used in most studies using chlo­
line) and absorption at 200–700 nm in its UV–Vis absorption spectrum. roform and trichloroacetic acid solutions. To ensure the selectivity the
It was discovered that 380 nm was the ideal wavelength for excitation of result of this measurement can be confirmed by using different con­
Cu-MOFs. On the other hand, at 427 nm, a notable fluorescence emission centrations of FFC on the sensor, and it has proven the high ability and
peak was observed at an excitation wavelength of 380 nm. Additionally, extraordinary sensitivity of this sensor in detection. We understand the
it was demonstrated by the evidence gathered that there is a significant sensitivity of Cu-MOFs by comparing the fluorescence peak from a
overlap between the UV–Vis absorption spectrum and the emission and standard concentration of 50 μM FFC solution with the fluorescence
fluorescence excitation spectra of Cu-MOFs. Consequently, the results result from a 50 μM spike on chicken meat, but the fluorescence results
demonstrated that the internal filter effect, or IFE mode, is applied be­ in the spike show that the interfering substances anyway, have been
tween the UV–Vis absorption spectrum and the Cu-MOFs. effective in the final result. Of course, with more experiments, the results
will be clearer, but due to device limitations, our analysis was limited.
This is a great advantage for designing the above sensor to detect this

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Table 2
Comparison of Cu-MOF sensing method with other methods to identify the residual antibiotics in different food samples.
Antibiotics Sensing materials Detection Method Linearity range LOD Sample Ref

Florfenicol Cu-MOF Fluorescence 2.5–50 μM 10.46 μM Chicken Present study

Florfenicol Mn:ZnS QDs Fluorescence 30–700 μmol L− 1 24 μM Chicken (Sadeghi et al., 2016)
Tetracycline Al-MOF@Mo/Zn-MOF Fluorescence 0.001–53.33 μM 0.53 nM Water (Li et al., 2020)
Ln-MOF (Tb-L1) Fluorescence 0.06–10 μg mL− 1 8 ng mL− 1 Water (Li et al., 2021)
Cr(III)-MOF Fluorescence 5–45 ng/mL 0.78 ng/mL Chicken Egg (Khezerlou, Tavassoli, Sani, et al., 2023)
1
Chloramphenicol MIP/Zr-LMOF luminescent 0.16_161.56 μg.L− 0.013 μg.L-1 Milk Honey (Amiripour et al., 2021)
zirconium-porphyrin MOF (PCN- Fluorescence 0.1 pg mL− 1 0.08 pg mL− 1 Milk shrimp (Liu et al., 2020)
222) 10 ng/mL
Ciprofloxacin Eu-MOF Fluorescence 0.1–18 μM 0.0136 μM Milk (Yue et al., 2022)

antibiotic. As is shown in Table 2, several studies conducted on other Acknowledgment

antibiotics, not reported in the diagnosis of FFC. In this study, by per­
forming various analyzes on Cu-MOFs, according to the study conducted The authors thanks to the Vice Chancellor for Research of Zanjan
by Huo et al., the results of our research showed that Cu-MOFs have University of Medical Sciences, IRAN for financial support of this proj­
higher thermal stability. In terms of the sensitivity and accuracy of the ect. (Project No: A-12-940-25, Ethics NO: IR.ZUMS.REC.1401.085).
designed Cu-MOFs sensor has the ability to detect antibiotics specifically
in with the lowest LOD, and also in terms of the stability time of the References
designed sensor, this sensor has shown its stability for 30 days.
Ahmadi, M., Ayyoubzadeh, S. M., Ghorbani-Bidkorbeh, F., Shahhosseini, S.,
Dadashzadeh, S., Asadian, E., … Siavashy, S. (2021). An investigation of affecting
4. Conclusions factors on MOF characteristics for biomedical applications: A systematic review.
Heliyon, 7(4), Article e06914. https://doi.org/10.1016/j.heliyon.2021.e06914
A novel Cu-MOF probe with excellent selectivity, high thermal sta­ Ahmadijokani, F., Molavi, H., Tajahmadi, S., Rezakazemi, M., Amini, M., Kamkar, M., …
Arjmand, M. (2022). Coordination chemistry of metal–organic frameworks:
bility, and chemical stability has been developed and synthesized in this Detection, adsorption, and photodegradation of tetracycline antibiotics and beyond.
work. The findings demonstrated that the addition of FFC results in an Coordination Chemistry Reviews, 464, Article 214562. https://doi.org/10.1016/j.
increase in fluorescence intensity. Additionally, Cu-MOF can success­ ccr.2022.214562
Al-Hashimi, B., Omer, K. M., & Rahman, H. S. (2020). Inner filter effect (IFE) as a simple
fully distinguish FFC from TET, CHL, ENR, ERY, PEN, and NEO. The and selective sensing platform for detection of tetracycline using milk-based
results demonstrate that this sensor's low LOD and quick response time nitrogen-doped carbon nanodots as fluorescence probe. Arabian Journal of Chemistry,
are its special qualities, making it appropriate for Cu-MOFs that are 13(4), 5151–5159. https://doi.org/10.1016/j.arabjc.2020.02.013
Ali, G. K., & Omer, K. M. (2022). Ultrasensitive aptamer-functionalized cu-MOF
designed to match high performance liquid chromatography results. Cu-
fluorescent nanozyme as an optical biosensor for detection of C-reactive protein.
MOFs with amine functionality can form hydrogen bonds with FFC, and Analytical Biochemistry, 658, Article 114928. https://doi.org/10.1016/j.
Cu-MOFs' fluorescence intensity can be increased by electron transfer ab.2022.114928
between Cu-MOFs and FFC. The Cu-MOFs sensor responds quickly and Alizadeh Sani, M., Jahed-Khaniki, G., Ehsani, A., Shariatifar, N., Dehghani, M. H.,
Hashemi, M., … Bayrami, Z. (2023). Metal–organic framework fluorescence sensors
has a broad pH and temperature detection range. These findings for rapid and accurate detection of melamine in milk powder. Biosensors, 13(1), 94.
demonstrate that Cu-MOFs is a very helpful and inspiring ideology for https://doi.org/10.3390/bios13010094
the development of fluorescent probes that detect antibiotics with Ameen, S. S. M., Mohammed, N. M. S., & Omer, K. M. (2023). Ultra-small highly
fluorescent zinc-based metal organic framework nanodots for ratiometric visual
notable selectivity. Moreover, Cu-MOFs serves as a practical fluores­ sensing of tetracycline based on aggregation induced emission. Talanta, 254, Article
cence probe that can be used for practical purposes such as detecting 124178. https://doi.org/10.1016/j.talanta.2022.124178
FFC in chicken meat. Ameen, S. S. M., Qader, I. B., Qader, H. A., Algethami, F. K., Abdulkhair, B. Y., &
Omer, K. M. (2024). Dual-state dual emission from precise chemically engineered bi-
ligand MOF free from encapsulation and functionalization with self-calibration
CRediT authorship contribution statement model for visual detection. Microchimica Acta, 191(1), 62. https://doi.org/10.1007/
s00604-023-06148-5
Amiripour, F., Ghasemi, S., & Azizi, S. N. (2021). Design of turn-on luminescent sensor
Roshanak Hasani: Writing – review & editing, Writing – original based on nanostructured molecularly imprinted polymer-coated zirconium
draft, Resources, Project administration, Investigation. Ali Ehsani: metal–organic framework for selective detection of chloramphenicol residues in milk
Writing – review & editing, Validation, Supervision, Methodology, and honey. Food Chemistry, 347, Article 129034. https://doi.org/10.1016/j.
foodchem.2021.129034
Formal analysis, Data curation, Conceptualization. Hassan Hassanza­
Cao, J. J., Fu, H. X., He, G. H., Meng, F.-J., Cai, D., Yuan, Z., & Luan, J. (2023). A stable
dazar: Writing – review & editing, Writing – original draft, Visualiza­ cu-MOF as a dual-functional sensor with high selectivity for fluorescence
tion, Supervision, Methodology, Funding acquisition, Formal analysis, enhancement and quenching. Journal of Solid State Chemistry, 327, Article 124300.
Data curation, Conceptualization. Majid Aminzare: Writing – review & https://doi.org/10.1016/j.jssc.2023.124300
Chou, K. F., & Dennis, A. M. (2015). Förster resonance energy transfer between quantum
editing, Visualization, Methodology. Arezou Khezerlou: Writing – re­ dot donors and quantum dot acceptors. Sensors, 15(6), 13288–13325. https://doi.
view & editing, Resources, Project administration, Investigation. org/10.3390/s150613288
Feng, S., Pei, F., Wu, Y., Lv, J., Hao, Q., Yang, T., Tong, Z., & Lei, W. (2021).
A ratiometric fluorescent sensor based on g-CNQDs@ Zn-MOF for the sensitive
Declaration of competing interest detection of riboflavin via FRET. Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy, 246, Article 119004. https://doi.org/10.1016/j.
The authors declare that they have no known competing financial heliyon.2021.e06914
Huo, P., Li, Z., Fan, C., & Pu, S. (2020). Amino-functionalized copper-based
interests or personal relationships that could have appeared to influence metal–organic frameworks for highly selective and sensitive detection of
the work reported in this paper. hypochlorite. New Journal of Chemistry, 44(45), 19753–19758. https://doi.org/
10.1039/D0NJ04256K
Hutchings, M. I., Truman, A. W., & Wilkinson, B. (2019). Antibiotics: Past, present and
Data availability future. Current Opinion in Microbiology, 51, 72–80. https://doi.org/10.1016/j.
mib.2019.10.008
Data will be made available on request. Jie, B., Lin, H., Zhai, Y., Ye, J., Zhang, D., Xie, Y., Zhang, X., & Yang, Y. (2023).
Mechanism, design and application of fluorescent recognition based on metal
organic frameworks in pollutant detection. Chemical Engineering Journal, 454, Article
139931. https://doi.org/10.1016/j.cej.2022.139931

8
R. Hasani et al. Food Chemistry: X 23 (2024) 101598

Kaur, A., Kaur, P., & Ahuja, S. (2020). Förster resonance energy transfer (FRET) and of a sensitive fluorescent aptasensor for specific detection of florfenicol in milk.
applications thereof. Analytical Methods, 12(46), 5532–5550. https://doi.org/ Talanta, 182, 193–201. https://doi.org/10.1016/j.talanta.2018.01.083
10.1039/D0AY01961E Sadeghi, S., Jahani, M., & Belador, F. (2016). The development of a new optical sensor
Khezerlou, A., Tavassoli, M., Khalilzadeh, B., Ehsani, A., & Kazemian, H. (2023). Metal- based on the Mn doped ZnS quantum dots modified with the molecularly imprinted
organic framework-based advanced sensing platforms for the detection of polymers for sensitive recognition of florfenicol. Spectrochimica Acta Part A:
tetracycline in food and water samples. Food Control. , Article 109965. https://doi. Molecular and Biomolecular Spectroscopy, 159, 83–89. https://doi.org/10.1016/j.
org/10.1016/j.foodcont.2023.109965 saa.2016.01.043
Khezerlou, A., Tavassoli, M., Sani, M. A., Ghasempour, Z., Ehsani, A., & Khalilzadeh, B. Seetharaj, R., Vandana, P., Arya, P., & Mathew, S. (2019). Dependence of solvents, pH,
(2023). Rapid and sensitive detection of tetracycline residue in food samples using molar ratio and temperature in tuning metal organic framework architecture.
Cr (III)-MOF fluorescent sensor. Food Chemistry: X, 20, Article 100883. https://doi. Arabian Journal of Chemistry, 12(3), 295–315. https://doi.org/10.1016/j.
org/10.1016/j.fochx.2023.100883 arabjc.2016.01.003
Li, C., Yang, W., Zhang, X., Han, Y., Tang, W., Yue, T., & Li, Z. (2020). A 3D hierarchical Shamsipur, M., Barati, A., & Nematifar, Z. (2019). Fluorescent pH nanosensors: Design
dual-metal–organic framework heterostructure up-regulating the pre-concentration strategies and applications. Journal of Photochemistry and Photobiology C:
effect for ultrasensitive fluorescence detection of tetracycline antibiotics. Journal of Photochemistry Reviews, 39, 76–141. https://doi.org/10.1016/j.
Materials Chemistry C, 8(6), 2054–2064. https://doi.org/10.1039/C9TC05941E jphotochemrev.2019.03.001
Li, R., Wang, W., El-Sayed, E.-S. M., Su, K., He, P., & Yuan, D. (2021). Ratiometric van Tran, T., Nguyen, D. T. C., Nguyen, T. T., Le, H. T., van Nguyen, C., & Nguyen, T. D.
fluorescence detection of tetracycline antibiotic based on a polynuclear lanthanide (2020). Metal-organic framework HKUST-1-based cu/Cu2O/CuO@ C porous
metal–organic framework. Sensors and Actuators B: Chemical, 330, Article 129314. composite: Rapid synthesis and uptake application in antibiotics remediation.
https://doi.org/10.1016/j.snb.2020.129314 Journal of Water Process Engineering, 36, Article 101319. https://www.sciencedirect.
Liu, S., Bai, J., Huo, Y., Ning, B., Peng, Y., Li, S., Han, D., Kang, W., & Gao, Z. (2020). com/science/article/abs/pii/S2214714420301987.
A zirconium-porphyrin MOF-based ratiometric fluorescent biosensor for rapid and Wang, B., Xie, X., Zhao, X., Xie, K., Diao, Z., Zhang, G., Zhang, T., & Dai, G. (2019).
ultrasensitive detection of chloramphenicol. Biosensors and Bioelectronics, 149, Development of an accelerated solvent extraction-ultra-performance liquid
Article 111801. https://doi.org/10.1016/j.bios.2019.111801 chromatography-fluorescence detection method for quantitative analysis of
Liu, X., Hu, M., Wang, M., Song, Y., Zhou, N., He, L., & Zhang, Z. (2019). Novel thiamphenicol, florfenicol and florfenicol amine in poultry eggs. Molecules, 24(9),
nanoarchitecture of co-MOF-on-TPN-COF hybrid: Ultralowly sensitive bioplatform of 1830. https://doi.org/10.3390/molecules24091830
electrochemical aptasensor toward ampicillin. Biosensors and Bioelectronics, 123, Wang, S., Ye, B., An, C., Wang, J., & Li, Q. (2019). Synergistic effects between cu
59–68. https://doi.org/10.1016/j.bios.2018.09.089 metal–organic framework (cu-MOF) and carbon nanomaterials for the catalyzation
Mansouri, M., Khalilzadeh, B., Barzegari, A., Shoeibi, S., Isildak, S., Bargahi, N., of the thermal decomposition of ammonium perchlorate (AP). Journal of Materials
Omidi, Y., Dastmalchi, S., & Rashidi, M.-R. (2020). Design a highly specific sequence Science, 54(6), 4928–4941. https://doi.org/10.1007/s10853-018-03219-4
for electrochemical evaluation of meat adulteration in cooked sausages. Biosensors Xia, L., Dou, Y., Gao, J., Gao, Y., Fan, W., Li, G., & You, J. (2020). Adsorption behavior of
and Bioelectronics, 150, Article 111916. https://doi.org/10.1016/j.bios.2019.111916 a metal organic framework of university in Oslo 67 and its application to the
Marimuthu, M., Arumugam, S. S., Sabarinathan, D., Li, H., & Chen, Q. (2021). Metal extraction of sulfonamides in meat samples. Journal of Chromatography A, 1619,
organic framework based fluorescence sensor for detection of antibiotics. Trends in Article 460949. https://doi.org/10.1016/j.chroma.2020.460949
Food Science & Technology, 116, 1002–1028. https://doi.org/10.1016/j. Xie, R., Yang, P., Liu, J., Zou, X., Tan, Y., Wang, X., Tao, J., & Zhao, P. (2021).
tifs.2021.08.022 Lanthanide-functionalized metal-organic frameworks based ratiometric fluorescent
Mohammed Ameen, S. S., Qasim, F. O., Alhasan, H. S., Hama Aziz, K. H., & Omer, K. M. sensor array for identification and determination of antibiotics. Talanta, 231, Article
(2023). Intrinsic dual-state emission zinc-based MOF rodlike nanostructures with 122366. https://doi.org/10.1016/j.talanta.2021.122366
applications in smartphone readout visual-based detection for tetracycline: MOF- Yue, X., Wu, C., Zhou, Z., Fu, L., & Bai, Y. (2022). Fluorescent sensing of ciprofloxacin
based color tonality. ACS Applied Materials & Interfaces, 15(39), 46098–46107. and chloramphenicol in milk samples via inner filter effect and photoinduced
https://doi.org/10.1021/acsami.3c11950 Electron transfer based on nanosized rod-shaped Eu-MOF. Foods, 11(19), 3138.
Sadeghi, A. S., Mohsenzadeh, M., Abnous, K., Taghdisi, S. M., & Ramezani, M. (2018). https://doi.org/10.3390/foods11193138
Development and characterization of DNA aptamers against florfenicol: Fabrication