Food Control 167 (2025) 110812

Contents lists available at ScienceDirect

Food Control
journal homepage: www.elsevier.com/locate/foodcont

A ratiometric fluorescent probe for the determination of quinolone

antibiotics in milk based on N and S co-doped carbon quantum dots
Fang Wang a, b, c , Xiaoyun Li a, b, c , Yuchen Zhang a, b, c , Hui Li a, b, c , Shanxue Jiang a, b, c ,
Jiajun Han d , Wenwen Gong e , Dandan Li a, b, c , Zhiliang Yao a, b, c, *
a
Department of Environmental Science and Engineering, Beijing Technology and Business University, Beijing, 100048, China
b
State Environmental Protection Key Laboratory of Food Chain Pollution Control, Beijing Technology and Business University, Beijing, 100048, China
c
China Food Flavor and Nutrition Health Innovation Center, Beijing Technology and Business University, Beijing, 100048, China
d
Department of Applied Chemistry, China Agricultural University, Beijing, 100193, China
e
Institute of Quality Standard and Testing Technology, BAAFS (Beijing Academy of Agriculture and Forestry Sciences), Beijing, 100097, China

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

Keywords: Quinolone antibiotics are widely used to prevent and treat diseases caused by bacterial infection. However,
Carbon quantum dot overuse of antibiotics may lead to their residue in the environment and food, posing potential threats to human
Ratiometric fluorescence probe health. In this study, a ratiometric fluorescent probe based on nitrogen and sulfur co-doped carbon quantum dots
Moxifloxacin
(N, S-CQDs) was synthesized, which can realize the detection of moxifloxacin (MXF), gatifloxacin (GAT) and
Gatifloxacin
Ofloxacin
ofloxacin (OFX) in milk. After addition of these antibiotics, the fluorescence at 440 nm originating from N, S-
Milk CQDs was significantly quenched due to the fluorescence resonance energy transfer (FRET), while the fluores-
cence at 525 nm (MXF), 500 nm (GAT) and 515 nm (OFX) were enhanced due to aggregation induced emission
(AIE). The fluorescence changes were completed within 30 s and stabilized for at least 14 days. Good linear
relationships between the fluorescence intensity ratios (F525/F440 for MXF, F500/F440 for GAT and F515/F440 for
OFX) and the antibiotic concentrations ranging from 0.1 to 100 mg L− 1 were obtained, with R2 above 0.99. The
limits of quantitation were in the range of 1.67–6.20 μg L− 1, and MXF, GAT and OFX can be well identified by
linear discriminant analysis. The probe enabled quantitative analysis of MXF, GAT and OFX in milk samples, with
recoveries ranging from 82% to 107%. A test strip based on the ratiometric fluorescence probe was successfully
applied for the detection of MXF and GAT in milk in combination with a smartphone. This method exerted high
specificity and sensitivity, which has the potential to achieve in-site detection of MXF, GAT and OFX in milk.

1. Introduction migratory goat milk in India, with the concentrations in the range of
43.3–115.1 μg L− 1 (A. Sharma & Kumar, 2024). It has been reported that
Quinolone antibiotics are a class of drugs with broad-spectrum MXF and GAT at actual environmental concentrations could promote the
antibacterial activity, which are widely used to prevent and treat dis- release of microcystin by Microcystis aeruginosa (Wan et al., 2021). GAT
eases caused by bacterial infection in humans and animals, such as could impair the cardiovascular system function of zebrafish, which
moxifloxacin (MXF), gatifloxacin (GAT) and ofloxacin (OFX) (A. Chen induce pericardial edema and cardiac dysfunction (Wan et al., 2021).
et al., 2022; J.-Y. Li et al., 2024; Song et al., 2024). However, quinolone Exposure of OFX affected nine successive generations (F1-F9) of Cae-
antibiotics are stable and difficult to be degraded and metabolized in the norhabditis elegans, with stimulating effect on F2 to F4 and inhibiting
environment and organisms. Overuse of quinolone antibiotics may lead effect on F5 to F9 generation (J. Zhang, Zheng, & Yu, 2022). It can be
to their residues in the environment and foods of animal origin, such as seen that quinolone antibiotic residues may pose enormous threats to
meat, eggs and milk (Chomthong et al., 2024; Liu et al., 2024; R. Sharma environment and human health. Therefore, analysis of quinolone anti-
et al., 2024). For instance, the maximum residual concentration of biotics in the environment and food is crucial for health risk assessment.
quinolone antibiotics in vegetable soils in Chongqing, China was 485.73 Traditional analytical methods can be used to detect quinolone an-
μg kg− 1 (Fang et al., 2023). Quinolone antibiotics were found in the tibiotics in the environment and food, such as high-performance liquid

* Corresponding author. Department of Environmental Science and Engineering, Beijing Technology and Business University, Beijing, 100048, China.
E-mail address: [email protected] (Z. Yao).

https://doi.org/10.1016/j.foodcont.2024.110812
Received 23 June 2024; Received in revised form 4 August 2024; Accepted 12 August 2024
Available online 13 August 2024
0956-7135/© 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
F. Wang et al. Food Control 167 (2025) 110812

chromatography (HPLC), capillary electrophoresis and electrochemical gatifloxacin (99.5%), ofloxacin (99.2%), tetracycline hydrochloride
methods (He, Lv, Yu, & Feng, 2010; Kheirandish et al., 2023; Yan, Zhou, (99.2%), oxytetracycline (99.5%), ampicillin (99.4%), sulfamethoxa-
Wang, & Huang, 2023; Yao, Song, Yan, & Chen, 2023). However, these zole (99.1%), sulfamethazine (98.9%), chlormequat (98.8%), boscalid
methods commonly require complex and time-consuming pretreatment (99.4%), dinotefuran (99.1%), novaluron (98.8%), cypermethrin
followed by usage of large instruments to achieve analysis, which cannot (99.4%), cyhalothrin (99.5%), bifenthrin (99.4%), propargite (99.5%)
meet the demand for timely detection of perishable food such as milk and flonicamid (99.1%) were purchased from Tmstandard Technology
(Balabin & Smirnov, 2011). Therefore, the development of a rapid, Co., Ltd. (Beijing, China). Chromatographic grade acetonitrile and
sensitive and simple method for the detection of quinolone antibiotics in analytical grade sulfuric acid (H2SO4) were from Shanghai Macklin
milk is of great significance for food safety and human health. Biochemical Co., Ltd (Shanghai, China) and Sinopharm Chemical Re-
Fluorescence analysis has received extensive attention because of its agent Co., Ltd. (Beijing, China), respectively. Milk was randomly pur-
advantages such as simple operation, high sensitivity, good selectivity, chased from the local markets in Beijing, China. Ultrapure water was
and rapidity (C.-Y. Wang, Sun, et al., 2022; Zhai et al., 2024). Carbon prepared by a Millipore purification system (Massachusetts, USA). The
quantum dots (CQDs) are considered ideal fluorescent probes for the standard solutions of antibiotics, pesticides and metal ions were pre-
detection of contaminants in the environment and food due to their high pared in acetonitrile or ultra-pure water and stored at 4 ◦ C before use.
fluorescence stability, good biocompatibility and low cost (Cao et al.,
2024; Y. Wang, Qin, et al., 2023; Yang et al., 2023). CQDs can be syn-
2.2. Synthesis of N, S-CQDs
thesized from a variety of carbon-containing materials. Doping with
heteroatoms (such as N, S, B and P) can adjust the charge and spin
N, S-CQDs was prepared by hydrothermal synthesis using citric acid
density of carbon atoms, provide more active sites, and enrich the en-
as carbon source and L-cysteine as nitrogen and sulfur sources. Citric
ergy level structure of CQDs, thereby enhancing their fluorescent per-
acid (1.92 g) and L-cysteine (4.04 g) were dissolved in 50 mL ultra-pure
formance (Cortes, Falomir, Lancis Saez, & Mínguez-Vega, 2024; Gao
water, and the mixture was transferred into an autoclave and reacted at
et al., 2024; Vyas, Jaiswal, Choudhary, Kodgire, & Joshi, 2024). For
200 ◦ C for 11 h. After cooling to room temperature, the solution was
instance, nitrogen-doped CQDs synthesized from pineapple peel and
passed through a 0.22 μm filter membrane, and the filtrate was dialyzed
diethylenetriamine by hydrothermal method can serve as a fluorescent
for 2–3 days to remove the remaining reactants.
probe for the detection of tetracycline in pork (C. Wang, Sun, et al.,
2022). Boron-doped CQDs prepared from citric acid and boric acid by
hydropyrolysis can be used as a fluorescent probe to detect amoxicillin 2.3. Characterization of N, S-CQDs
(X. Zhang, Ren, Ji, & Fan, 2020). Sulfur-doped CQDs were synthesized
with citric acid and sodium sulfide, which can achieve the specific The absorbance of N, S-CQDs was recorded by UV–Vis spectropho-
detection of trace Hg2+ in tap water (Wang et al., 2019). Linear tometer Evolution 300 (Shimadzu, Japan). The fluorescence spectra of
Discriminant Analysis (LDA) is a statistical classification technique that N, S-CQDs were measured by fluorescence spectrophotometer RF-6000
projects high-dimensional data into a lower-dimensional space, maxi- (Shimadzu, Japan). The morphology and particle size distribution of
mizing the separation between different groups. The combination of N, S-CQDs were observed by transmission electron microscope (TEM)
multi-emission fluorescent probes with LDA allows for the JEM-F200 (JEOL, Japan). The crystalline structure of N, S-CQDs was
high-specificity identification and rapid detection of multiple sub- characterized by Bruker D8 Advance diffractometer. The surface func-
stances. For instance, a sensitized ratiometric fluorescence probe based tional groups of N, S-CQDs were measured by Fourier Transform
on N, S co-doped CQDs and mercaptoacetic acid-capped CdTe quantum Infrared Spectroscope (FTIR) NicoletiS10 (Thermo Fisher Scientific,
dots was developed, which can accurately recognize single and mixed USA). The elemental composition of N, S-CQDs was explored by X-ray
tetracyclines, including tetracycline, oxytetracycline, chlortetracycline photoelectron spectroscope (XPS) Escalab 250Xi (Thermo Fisher Sci-
and doxycycline in the combination with LDA model (Fan et al., 2023). entific, USA). Fluorescence lifetime was obtained by Stable Transient
In this study, nitrogen and sulfur co-doped CQDs (N, S-CQDs) emit- Fluorescence Spectrometer Fluoro Max-Plus (HORIBA, USA).
ting bright blue fluorescence were synthesized from citric acid and L- The fluorescence quantum yield (QY) of N, S-CQDs was calculated by
cysteine, which can be used as ratiometric fluorescent probes for the using 0.1M quinine sulfate as the standard:
rapid detection of MXF, GAT and OFX in milk. After addition of MXF,
I AR n2
GAT or OFX, the fluorescence at 440 nm was quenched due to the ab- QY = QYR × × ×
sorption of N, S-CQDs excitation light by MXF, GAT and OFX. And the IR A n2R
-OH, -COOH and -NH2 groups on the surface of N, S-CQDs can form
Where QY and QYR were the quantum yields of N, S-CQDs and quinine
hydrogen bonds with quinolone antibiotics, leading to the fluorescence
sulfate (54%), respectively; I and IR were the integrated fluorescence
at 525 nm (MXF), 500 nm (GAT) and 515 nm (OFX) enhanced due to the
intensity of N, S-CQDs and quinine sulfate, respectively; n and nR were
aggregation induced emission. Good linear relationships between the
the refractive indices (1.33 for both water and 0.1 M sulfuric acid) of
fluorescence intensity ratios (F525/F440, F500/F440 and F515/F440) and the
water and 0.1 M sulfuric acid, respectively; A and AR were the absor-
concentrations of quinolone antibiotics were obtained in the range of
bances of N, S-CQDs and quinine sulfate at the same excitation wave-
0.1–100 mg L− 1. MXF, GAT and OFX can be well recognized based on
length, which were below 0.05 in order to avoid the self-priming effect.
LDA model. Besides, test strips were prepared based on the ratiometric
fluorescent probe, and the quinolone antibiotics in milk can be analyzed
in combination with smartphone, proving this method has the potential 2.4. Ratiometric fluorescence detection based on N, S-CQDs
to achieve real-time detection of MXF, GAT and OFX in milk.
After addition of 1.2 mL MXF, GAT and OFX solution into 4 mL probe
2. Materials and methods solution, which was prepared by diluting N, S-CQD solution by 10 times,
the fluorescence emission intensities at 440 nm (F440), 500 nm (F500),
2.1. Chemicals and reagents 515 nm (F515) and 525 nm (F525) were measured at the excitation
wavelength of 380 nm, and the fluorescence intensity ratios F525/F440,
Citric acid, L-cysteine, quinine sulfate, NaCl, KCl, CaCl2, CdCl2, F500/F440 and F515/F440 were calculated. The experiment was repeated
CrCl3, HgNO3, CoCl2, MgCl2, CuCl2, ZnCl2, FeCl2, FeCl3, NiCl2, PbCl2, for three times. LODs were calculated by LOD = 3σ/S (σ was the stan-
AlCl3, BaCl2 and AgCl were bought from Shanghai Macklin Biochemical dard deviation of 10 blank samples, and S was the slope of the standard
Co., Ltd. (Shanghai, China). Standards of moxifloxacin (purity 99.3%), curve). LOQs were calculated by LOQ = 10LOD/3.

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F. Wang et al. Food Control 167 (2025) 110812

2.5. Selectivity evaluation concentrations.

Antibiotics (tetracycline hydrochloride, oxytetracycline, ampicillin, 3. Results and discussion

sulfamethoxazole and sulfamethazine), pesticides (bifenthrin, cyhalo-
thrin, chlormequat, boscalid, dinotefuran, flonicamid, novaluron, 3.1. Characterization of N, S-CQDs
cypermethrin, propargite) and metal ions (Na+, K+, Ca2+, Cd2+, Cr3+,
Hg2+, Co2+, Mg2+, Cu2+, Zn2+, Fe2+, Fe3+, Ni2+, Pb2+, Al3+, Ba2+ and As shown in Fig. 1A, N, S-CQD displayed transparent and colorless
Ag+) solution at concentration of 50 mg L− 1 were used to evaluate the solution under daylight light, which emit bright blue fluorescence under
selectivity of the fluorescence probe. F440, F500, F515 and F525 were UV lamp with the excitation wavelength of 365 nm. The maximum
measured at the excitation wavelength of 380 nm, and the fluorescence excitation wavelength and emission wavelength of N, S-CQD were 380
intensity ratios F525/F440, F500/F440 and F515/F440 were calculated. The nm and 440 nm, respectively. Fluorescence quantum yield is an
experiment was conducted in triplicate. important index of luminescence efficiency, with higher quantum yield
indicating higher efficiency of converting light energy into fluorescence.
2.6. Recovery experiment in milk samples The relative quantum yield of N, S-CQDs was up to 31% (Table S1),
indicating high luminescence efficiency. The characteristic functional
Biomacromolecule in milk such as fat and protein may be adsorbed groups of N, S-CQDs were measured by FTIR. It can be seen in Fig. 1B,
on the surface of quantum dots, which can interfere with the binding of stretching vibrations of O-H or N-H (3334 cm− 1) and C=O (1649 cm− 1)
antibiotics and quantum dots, affecting the accuracy of results. There- were observed. As shown in Fig. 1C that N, S-CQDs were uniformly
fore, pretreatment of milk sample is of great necessity. After addition of spherical particles with an average diameter of 3.8 nm. N, S-CQDs were
5 mL acetonitrile and 2 g NaCl to 5 mL milk, the mixture was centrifuged well dispersed in water, and no obvious agglomeration were observed.
at 10000 rpm for 3 min, and the supernatant was filtered through 0.22 The X-ray diffraction (XRD) pattern of N, S-CQDs (Fig. 1D) showed a
μm membrane. F440, F500, F515 and F525 were measured at the excitation broad diffraction peak at 2θ = 29.40◦ corresponding to the (002)
wavelength of 380 nm after addition of MXF, GAT and OFX, and the diffraction plane of graphitic carbon, revealing its amorphous nature
fluorescence intensity ratios F525/F440, F500/F440 and F515/F440 were along with a low degree of crystallinity. Elements of N, S-CQDs were
calculated. The experiment was conducted in triplicate. analyzed by XPS spectrum. The peaks at 163.7 eV, 284.9 eV, 400.0 eV
and 531.4 eV were ascribed to S2p, C1s, N1s and O1s, respectively
(Fig. 1E). There are three fitting peaks in the XPS spectrum of C1s
2.7. Smartphone-assisted detection based on fluorescent test strip (Fig. S1A), corresponding to C-C/C=C (284.8 eV), C-O/C-N (286.1 eV)
and C=O (288.7 eV). The XPS spectrum of O1s (Fig. S1B) can be
The test strip was prepared by dripped with 2 mL of the probe so- deconvoluted into two peaks at 531.1 eV and 532.6 eV, which
lution onto the filter paper and dried. After dripping 20 μL of milk contributed to C=O and C-O, respectively. The N1s spectrum (Fig. S1C)
extraction solution onto the test strip, photos were taken using the revealed two peaks at 399.9 eV and 401.4 eV, highlighting C-N and N-H,
default camera app of a smartphone (iPhone 12) under a UV lamp with respectively (Fig. S1D). There are two fitting peaks in the XPS spectrum
the excitation wavelength of 365 nm. The RGB values of the fluorescent of S2p, corresponding to C-S-C S2P3/2 (163.5 eV) and C-S-C S2P1/2 (164.6
color of the test strip were identified by Image J software. The ratios of eV). The above results proved that CQDs were successfully doped with N
green to blue values (G/B) were used to determine MXF and OFX

Fig. 1. (A) UV absorbance and fluorescence spectra; (B) FTIR spectrum; (C)TEM image and particle size distribution; (D) XRD image; and (E) XPS spectrum of N,
S-CQDs.

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and S elements, and the surface of N, S-CQDs contained hydrophilic detection limits.
groups such as hydroxyl, carboxyl or amino groups, providing good The recognition ability of N, S-CQD ratiometric fluorescent probes
water solubility. for different quinolone antibiotics was evaluated, including single and
The synthesis conditions for N, S-CQDs were optimized according to mixed quinolone antibiotics. The fluorescence intensities at 440 nm,
fluorescence intensity, including the molar ratio (citric acid: L-cysteine), 500 nm, 515 nm and 525 nm from different groups, with six replicates
synthesis temperature and reaction time. As shown in Fig. S2B, the each group, were used to construct the LDA model. As shown in Fig. 3,
fluorescence intensity of N, S-CQDs increased with the molar ratio the separation of single and mixed quinolone antibiotics in aqueous
increased from 0.1 to 0.3, however, decreased with the molar ratio solution can be realized using the LDA model, with classification accu-
increased from 0.3 to 0.5, which reached the highest value when the racy rates greater than 0.989, which demonstrates the potential for
molar ratio was 0.3. The fluorescence intensity of N, S-CQDs gradually detecting different quinolone antibiotics.
increased with the temperature increased from 120 ◦ C to 200 ◦ C Currently, single-signal fluorescent probes have been successfully
(Fig. S2C). It can be seen from Fig. S2D that the fluorescence intensity of applied to the detection of quinolone antibiotics. For example, a fluo-
N, S-CQDs increased with the synthesis time increased from 9 to 10 h, rescence sensor based on metal–organic framework (MOF) [Co
and then reached a plateau. Therefore, the synthesis condition param- (apba)2(H2O)2] can achieve detection of MXF in milk, with fluorescence
eters of N, S-CQDs were chosen as follow: molar ratio of citric acid to L- at 382 nm being quenched upon the addition of MXF (Tan et al., 2023).
cysteine of 0.3, temperature at 200 ◦ C, and synthesis time of 11 h. A fluorescence probe based on bovine serum capped ZnS nanoparticles
(ZnS NPs) was developed for the detection of GAT, whose fluorescence
3.2. Ratiometric fluorescent probe for the detection of quinolone at 296 nm can be quenched by GAT (L. Li et al., 2013). Green copper
antibiotics nanoclusters coated with sodium gluconate (Gl@Cu NCs) can be used as
a fluorescence probe for the detection of OFX, with the fluorescence at
N, S-CQDs were used as ratiometric fluorescent probes for the 414 nm being significantly enhanced in the presence of OFX (Moham-
detection of MXF, GAT and OFX. The fluorescence emission spectrum of mad Hosseini & Sadeghi, 2024). However, single-signal fluorescent
N, S-CQDs was shown in Fig. S2A. The maximum emission wavelength analysis suffers from low specificity and poor anti-interference ability,
of N, S-CQDs was 440 nm, which was shifted to 525 nm, 500 nm and which may be easily affected by the background and probe concentra-
515 nm after addition of MXF, GAT and OFX, respectively. Fig. 2 showed tion, resulting in false positive results. Dual-signal fluorescent probes
the fluorescence intensity of N, S-CQDs with varying concentrations of exert superior anti-interference capabilities. Their fluorescence in-
MXF, GAT and OFX. It can be seen that the fluorescence intensity at 440 tensities in different emission bands change simultaneously, thereby the
nm was gradually decreased, while the fluorescence intensities at 525 false positive results and detection error caused by background inter-
nm (MXF), 500 nm (GAT), and 515 nm (OFX) gradually increased with ference and other factors can be reduced according to the relative
the increase of quinolone antibiotic concentration. Good linear re- fluorescence intensity ratio. For instance, a fluorescence probe based on
lationships between the fluorescence intensity ratios (F525/F440, F500/ CQDs derived from polyvinyl alcohol was developed, whose fluores-
F440 and F515/F440) and the concentrations of MXF, GAT and OFX cence at 372 nm was quenched and the fluorescence at 508 nm was
ranging from 0.1 to 100 mg L− 1 were found, with the R2 greater than enhanced after addition of MXF, therefore, quantification of MXF in milk
0.9893 (Table S2). The LODs of MXF, GAT and OFX were 0.33, 0.57 and and eggs can be achieved according to fluorescence intensity ratio
0.77 μg L− 1, and the LOQs were 1.11, 1.90 and 2.56 μg L− 1, respectively. (F508/F372) (Sajwan, Kumar Himanshu, & Solanki, 2024). The real-time
The results suggested that the N, S-CQD ratiometric fluorescent probe detection of OFX in daily drink was realized based on tri-doped gra-
could achieve the quantitative analysis of MXF, GAT and OFX with low phene quantum dots (T-GQDs) ratiometric fluorescence probe (C. Wang,

Fig. 2. Fluorescence emission spectra of N, S-CQDs after addition of different concentrations of (A) MXF, (B) GAT and (C) OFX.

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Fig. 3. Discrimination result of the fluorescence response identification results of MXF, GAT, and OFX in (A) aqueous solution and (B) milk samples.

Qin, et al., 2023). The fluorescence at 414 nm was quenched, and the (F525/F440, F500/F440 and F515/F440). Compared with other methods
fluorescence at 498 nm was enhanced by the presence of OFX, and good (Table 1), the ratiometric fluorescence probe method based on N,
linear relationship between the fluorescence intensity ratio (F498/F414) S-CQDs in this study has a wider linear range and a lower detection limit
and OFX concentration was observed. In this study, N, S-CQDs for the detection of MXF, GAT, and OFX.
dual-signal fluorescence probe was developed, which can selectively
detect MXF, GAT, and OFX based on the fluorescence intensity ratios

Table 1
Comparison of MXF, GAT, and OFX detection methods.
Methods Pollutants Matrices Linear ranges LODs References
(μM) (nM)

Deep UV-resonance Raman spectroscopy MXF Plasma 10–1000 4000 Domes, Popp, Hagel, Pletz, and Frosch
(2023)
Electrochemical sensor based on MIPa MXF Urine 10–1000 1700 Hammam, Wagdy, and El Nashar (2018)
Electrochemical sensor based on CuNPsb and MWCNTsc MXF Pork 5–1000 205 Song et al. (2024)
Electrochemical sensor based on cysteic acid/CPEd GAT Serum 0.02–200 10 (F. Zhang, Gu, Ding, Li, & Liu, 2013)
OFX Serum 0.06–10 20
Electrochemical sensor based on β-CD/rGO/GCE e GAT Urine 0.05–150 20 (Z. Jiang, Li, & Zhang, 2016)
Electrochemical sensor based on MoS2@MWCNTf OFX Water 0.29-0.82 120 (R. Sharma et al., 2024)
Electrochemical sensor based on ASBA g and GRh OFX Drug 0.1–40 30 Si et al. (2020)
Electrochemical sensor based on CFO/GCEi OFX Urine 1–55 60 Manjula, Pulikkutty, Chen, Chen, and Liu
(2021)
Electrochemiluminescence sensor based on CuS-rGO/g- GAT Plasma 0.01–100 3.5 (L. Jiang et al., 2019)
C3N4-GCEj
Fluorescent sensor based on MOF MXF Water 0–100 43 Tan et al. (2023)
Fluorescence sensor based on Eu-MOFk OFX Water 0–33 2400 (J.-Y. Li et al., 2024)
Fluorometric probe based on polyvinyl alcohol-derived MXF Milk 0.025–15 6.3 Sajwan et al. (2024)
CQDs
Fluorometric probe based on ZnS NPsl GAT Water 0.2–100 65 (L. Li et al., 2013)
Fluorescent probe based on Gl@Cu NCsm OFX Milk, urine and serum 0.014-0.83 8 Mohammad Hosseini and Sadeghi (2024)
Fluorescent probe based on 2,3-CQDs and 1,8-CQDsn OFX Serum 0–120 460 (Rateb, Ghubish, Abdel Hakiem, &
El-Kemary, 2023)
Fluorescent probe based on T-GQDs o OFX Juice, carbonated 0–30 46 (C. Wang, Qin, et al., 2023)
drink, milk
HPLC–UV MXF Plasma 0.04–249 24.9 Khan et al. (2016)
OFX 0.04–55 22.1
HPLC–UV GAT Drug 10.7–107 1351 Aljuffali, Kalam, Sultana, Imran, and
Alshamsan (2015)
Spectrophotometric analysis based on La(III) ions GAT Water 50–300 2877 (Mostafa, Abd El-Wahab, Salman, &
Abdelbaset, 2021)
Synchronous fluorescence spectroscopy coupled with OFX Duck meat 3.5–76.1 3459 (J. Chen, Liu, Yuan, Chen, & Zhao, 2021)
chemometric methods
Fluorometric probe based on N, S-CQDs MXF Milk 0.249–249 1.3 This study
GAT 0.266–266 3.2
OFX 0.277–277 5.2
a
MIP represented molecularly imprinted polymer.
b
CuNPs represented nano-flower structured copper nanoparticles.
c
MWCNTs represented multi-walled carbon nanotubes.
d
Cysteic acid/CPE represented cysteic acid modified carbon paste electrode.
e
β-CD/rGO/GCE represented β-cyclodextrin (β-CD) and reduced-graphene oxide (rGO) modified glassy carbon electrode (GCE).
f
MoS2@MWCNT represented molybdenum disulfide nanostructure grown on multi-walled carbon nanotube.
g
ASBA represented p-aminobenzene sulfonic acid.
h
GR represented graphene.
i
CFO/GCE represented disposable glassy carbon electrode modified by ceramic cerium ferrite CeFeO3.
j
CuS-rGO/g-C3N4-GCE represented reduced graphene oxide-copper sulfide-carbon nitride nanosheets composite.
k
Eu-MOF represented europium(III) metal-organic framework.
l
NPs represented nanoparticles.
m
Gl@Cu NCs represented copper nanoclusters coated with sodium gluconate.
n
2,3-CQDs and 1,8-CQDs represented CQDs synthesized from 2,3-diaminonaphthalene and 1,8-diaminonaphthalene, respectively.
o
T-GQDs represented tri-doped graphene quantum dots.

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3.3. Optimization of the detection conditions 3.5. Fluorescence quenching and enhancement mechanism

The response time and pH were optimized by monitoring the fluo- In order to investigate the fluorescence quenching mechanism, the
rescence ratios (F525/F440, F500/F440 and F515/F440). After addition of fluorescence lifetimes of N, S-CQDs were measured. As shown in Fig. 6A,
MXF, GAT and OFX, the fluorescence ratios increased rapidly within 30 s the fluorescence lifetime of N, S-CQDs was 10.28 ns, which significantly
and remained stable within 30 min (Fig. 4A). Therefore, the reaction decreased to 7.27, 9.84 and 9.01 ns after addition of MXF, GAT, and
time was set as 3 min in this study. The influence of pH on the fluo- OFX, respectively. Dynamic quenching may lead to the decrease of
rescence ratios of N, S-CQDs was assessed after adjusting the pH with fluorescence lifetime, however, the calculated dynamic quenching
HCl or NaOH. When the pH ranged from 4 to 14, the fluorescence ratios constant (5.4 × 1011 - 2.8 × 1012 mol− 1 s− 1) were obviously greater than
remained stable in the presence of MXF, GAT and OFX (Fig. 4B). the maximum dynamic quenching constant (2 × 1010 mol− 1 s− 1). The
Considering the pH of the solution was in the range of 4–5, no additional fluorescence excitation and emission spectra of N, S-CQDs, and ultra-
pH adjustment was conducted. violet absorbance spectrum of MXF, GAT, and OFX were demonstrated
The fluorescence stability of N, S-CQDs was evaluated based on its in Fig. 6B. It can be seen that the absorbance spectrum of MXF, GAT, and
fluorescence response toward quinolone antibiotics at room tempera- OFX obviously overlapped with the fluorescence excitation spectrum of
ture (25 ◦ C) and 4 ◦ C. As shown in Fig. 4C and D, the fluorescence in- N, S-CQDs, indicating MXF, GAT and OFX can absorb the excitation light
tensity ratios of N, S-CQDs did not change significantly within 14 days at of N, S-CQDs. These results suggested fluorescence resonance energy
4 ◦ C and room temperature. These results demonstrated the highly transfer (FRET) between N, S-CQDs and MXF/GAT/OFX occurred,
stable N, S-CQD fluorescent probe has a sensitive and rapid response to resulting in N, S-CQD fluorescence at 440 nm quenched. The functional
MXF, GAT and OFX, which ensured the accuracy of the results. groups -OH, -COOH and -NH2 on the surface of N, S-CQDs may form
hydrogen bonds with MXF, GAT and OFX, and the fluorescence at 525
3.4. Selectivity evaluation nm (MXF), 500 nm (GAT) and 515 nm (OFX) were enhanced due to the
aggregation induced emission.
The selectivity of the fluorescence probe was evaluated by adding 50
mg L− 1 antibiotics (tetracycline hydrochloride, oxytetracycline, ampi-
cillin, sulfamethoxazole and sulfamethazine), pesticides (bifenthrin, 3.6. Detection of milk samples
cyhalothrin, chlormequat, boscalid, dinotefuran, flonicamid, novaluron,
cypermethrin, propargite) and metal ions (Na+, K+, Ca2+, Cd2+, Cr3+, Recovery experiments of the N, S-CQD fluorescent probe were con-
Hg2+, Co2+, Mg2+, Cu2+, Zn2+, Fe2+, Fe3+, Ni2+, Pb2+, Al3+, Ba2+ and ducted at three spiked concentrations (0.1, 1 and 10 mg L− 1). Satisfac-
Ag+) into the probe solution. As displayed in Fig. 5, the fluorescence tory recoveries of MXF, GAT and OFX were obtained, ranging from 85 to
ratios F525/F440, F500/F440 and F515/F440 were only significantly 109%, with RSD less than 3.9% (Table S3). Good linear relationships
increased after addition of 5 mg L− 1 MXF, GAT, and OFX, indicating the between the fluorescence intensity ratios and the concentrations of MXF,
fluorescent probe had good selectivity for MXF, GAT, and OFX. GAT, and OFX in milk were found, with R2 greater than 0.9969
(Table S2). The LODs of MXF, GAT, and OFX in milk were 0.50, 0.12 and
0.19 μg L− 1, respectively. The accuracy of N, S-CQD fluorescent probe
was verified by traditional HPLC method, and the results obtained by

Fig. 4. Fluorescence intensity ratios (F525/F440, F500/F440 and F515/F440) of N, S-CQDs (A) within 30 min; (B) at different pH; (C) within 14 days at room temperature;
and (D) within 14 days at 4 ◦ C after addition of MXF, GAT, and OFX.

6
F. Wang et al. Food Control 167 (2025) 110812

1 1
Fig. 5. Fluorescence intensity ratios of (A) F525/F440; (B) F500/F440; and (C) F515/F440 after addition of 5 mg L− MXF, GAT, and OFX and 50 mg L− antibiotics,
pesticides or metal ions.

Fig. 6. (A) Fluorescence lifetime decay curves of N, S-CQDs before and after addition of MXF, GAT and OFX; (B) Fluorescence excitation and emission spectra of N, S-
CQDs, and ultraviolet absorbance spectra of MXF, GAT and OFX.

HPLC were consistent with those obtained by N, S-CQD fluorescent quinolone antibiotics in complex mixed actual samples.
probe, indicating the reliability of the N, S-CQD fluorescent probe in the
detection of milk. As shown in Fig. 3B, a LDA model enabled the sepa-
3.7. Fluorescence test strip
ration of single and mixed quinolone antibiotics from milk samples,
achieving classification accuracy rates above 0.983. Therefore, the N, S-
A test strip based on N, S-CQD fluorescent probes was developed,
CQD ratiometric fluorescence probes have potential to analyze
which can achieve semiquantitative analysis of MXF and OFX in milk in

7
F. Wang et al. Food Control 167 (2025) 110812

the combination of smartphone. As shown in Fig. 7, the color of the test

strip under ultraviolet lamp gradually changed from bright blue to light
green with the MXF concentration increased, which changed from bright
blue to light blue with the OFX concentration increased. However, the
color of the test strip under ultraviolet lamp has no obvious change
before and after addition of GAT. And the relationships of the color and
concentrations of MXF and OFX were further investigated. Satisfactory
linear relationships between the G/B values and the concentration of
MXF (in the range of 0.2–2 mg L− 1), and the concentration of OFX (in the
range of 0.1–3 mg L− 1) were found (Table S4). Therefore, the concen-
trations of MXF and OFX in milk can be evaluated according to the
fluorescent color under ultraviolet lamp combined with the smartphone.
The method is simple and economical, which has the potential for in situ
and real-time detection of MXF and OFX in milk. Fig. 7. Fluorescence test strip results of (A) MXF and (B) OFX in milk samples
under UV lamp.
4. Conclusion
Data availability
In this study, N, S-CQDs emitting bright blue fluorescence were
synthesized by citric acid and L-cysteine, which can be used as ratio- Data will be made available on request.
metric fluorescent probes to achieve rapid detection of MXF, GAT, and
OFX in milk. Due to the fluorescence resonance energy transfer and Appendix A. Supplementary data
aggregation induced emission, the blue fluorescence at 440 nm was
significantly quenched and the green fluorescence at 525 nm, 500 nm Supplementary data to this article can be found online at https://doi.
and 515 nm were enhanced after addition of MXF, GAT, and OFX, org/10.1016/j.foodcont.2024.110812.
respectively. Excellent fluorescence stability of N, S-CQDs was observed
under different temperature and pH value. There was a good linear References
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