Microchemical Journal 194 (2023) 109283

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Sensitive and smartphone-assisted visual detection of oxytetracycline by a

ratiometric fluorescence sensor based on nitrogen-doped carbon quantum
dots from banana peel cooperating with europium
Chen Wu , Tong Zhou , Zhe Gao , Meijiao Li , Qian Zhou *, Wen Zhao *
College of Food Science and Technology, Hebei Agricultural University, Baoding 071001, Hebei, PR China

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

Keywords: Oxytetracycline (OTC) residues have serious adverse effects on human health. Thus, selective and sensitive field
Food processing waste detection methods are needed. Here, we successfully synthesized nitrogen-doped carbon quantum dots (N-CQDs)
Lanthanides with good water-solubility, prominent fluorescence (FL), and favorable stability via a one-step hydrothermal
Nitrogen-doped carbon quantum dots
method using banana peel as a carbon source and diethylenetriamine as a nitrogen source. We used the N-CQDs
Oxytetracyclines
Pork samples
to create a ratiometric FL probe by self-assembling them with europium ions (Eu3+), enabling OTC detection. The
Ratiometric fluorescence detection FL intensity of N-CQDs at 445 nm was quenched due to the inner filter effect, while the FL intensity of Eu3+ at
621 nm markedly increased via the antenna effect upon OTC introduction. The ratiometric FL sensor demon­
strated two linear relationships with OTC concentrations, ranging from 0.01 to 5 μg mL− 1 and 5 to 25 μg mL− 1,
with a limit-of-detection of 4.9 ng mL− 1 for OTC. Additionally, this platform depicted an apparent color change
from blue to purple under a 365 nm ultraviolet–visible lamp, and a visual semi-quantitative analysis of OTC was
achieved using a mobile phone application. We successfully implemented this method to detect OTC in pork
muscle and swine urine, achieving remarkable recovery results (96.89–103.20%). Therefore, our findings
demonstrate the potential of this approach for real-time and semi-quantitative OTC detection.

1. Introduction biomass materials, such as orange juice, watermelon juice, and lemon
juice as precursors [12]. Among them, food processing waste, including
Oxytetracycline (OTC) is a member of the versatile tetracycline class peels [13], roots [14], and kernels [15], have aroused great interest as
of antibiotics that is extensively employed in treating and preventing input materials for preparing CQDs due to their economic and envi­
illnesses in animals and humans by interfering with protein synthesis ronmental advantages. Nevertheless, the relatively low quantum yields
[1,2]. Nevertheless, overdose or long-term low-dose OTC use can result (QY) of CQDs prepared using hydrothermal method have limited their
in residues in food, water, the environment, and soils that are difficult to application [16]. Doping of hetero atoms may substantially improve this
degrade and pose serious threats to human health, including liver problem [17]. To this end, nitrogen atoms have been effectively applied
damage, allergic reactions, and bacterial resistance [3,4]. to prepare doped-CQDs (N-CQDs), which demonstrated good solubility,
Carbon quantum dots (CQDs) were serendipitously discovered as a sensitive selectivity, excellent stability, and good bio-compatibility with
new class of fluorescent carbon nanoparticles in 2004 [5] and officially high QY [18–20].
named in 2006 [6]. CQDs have gained increasing attention for their The lanthanides have a wide range of applications in analytical
promising applications in fields of rapid detection due to various merits, chemistry, biomedicine, and functional materials due to their unique
such as good fluorescence (FL) stability, favorable bio-compatibility, physical, chemical, and optical properties such as a narrow emission
wide excitation range, superior water dispersibility, and low cost band, large Stokes shift, long FL lifetime, and high luminescence in­
[7–9]. The hydrothermal method is widely used for preparing CQDs due tensity [21,22]. Common lanthanide elements are europium (Eu3+)
to its advantages of reaction simplicity, low energy consumption, and [23,24], terbium (Tb3+) [25,26], lanthanum [27], etc. Among them,
eco-friendly applications [10,11]. Recently, researchers have exten­ Eu3+ has excellent red FL emission characteristics accompanied by
sively studied the hydrothermal method for CQDs preparation using nanomaterials when detecting target substances. Complexes formed

* Corresponding authors at: Lekai South Street 2596, Baoding 071001, PR China.
E-mail addresses: zhouqian@hebau.edu.cn (Q. Zhou), zhaowen@hebau.edu.cn (W. Zhao).

https://doi.org/10.1016/j.microc.2023.109283
Received 30 June 2023; Received in revised form 23 August 2023; Accepted 29 August 2023
Available online 3 September 2023
0026-265X/© 2023 Elsevier B.V. All rights reserved.
C. Wu et al. Microchemical Journal 194 (2023) 109283

using Eu3+ and CQDs as FL probes have gained attention for use in rapid In this study, we developed an N-CQDs/Eu3+-based ratiometric FL
detection methods [24]. For example, Abdel-Lateef et al. developed sensor for OTC detection, providing a tool for rapid visual detection
Eu3+-doped carbon dots with unique FL properties to selectively detect (Scheme 1). We utilized smartphones as a platform for real-time, fast,
metanil yellow dye in turmeric [28]. Wu et al. designed a nano­ and visual sensing of OTC, offering a promising approach for qualitative
fluorescent probe based on nitrogen-doped carbon dots and Eu3+ to identification and semi-quantitative analysis of OTC. We validated the
selectively detect OTC in water and milk samples [29]. Notably, the utility of the ratiometric FL sensor by examining pork samples and
complexes formed by Eu3+ and ancillary ligands can exhibit distinct performing point-of-care testing using the smartphone-assisted N-CQDs/
color changes and facilitate convenient visual detection. Jia et al. Eu3+-based ratiometric FL sensor, which holds a broad application
designed a mobile phone-assisted visual FL platform using CQDs and prospect in food safety and environmental monitoring.
Eu3+ to provide a real-time detection strategy for the selective detection
of tetracycline (TC) in pure milk [30]. Additionally, Yang et al. devel­ 2. Materials and methods
oped a dual-emitting ratiometric FL sensor for TC, OTC, and doxycycline
(DOX) based on boron N-CQDs and Eu3+ [31]. In addition, Tb3+ is also a 2.1. Materials
rare earth element that is widely used in the detection of biological
environments [32,33]. For example, Tb3+ could be applied as a kind of Bananas were purchased from the local market in Baoding, China.
sensitive luminescence method for detecting deferiprone in urine and Banana peels were collected and processed into powder through
serum and the noninvasive bioimaging of HeLa cancer cells [34,35]. lyophilization in FD-304 (Shandong, China). Diethylenetriamine
Gas chromatography-mass spectrometry [36], high-performance (DETA) was purchased from Shanghai Acmec Biochemical Co., Ltd.
liquid chromatography [37], capillary electrophoresis [38], electro­ (Shanghai, China). OTC, TC, DOX, chlortetracycline (CTC), florfenicol
chemical [39], enzyme-linked immunosorbent assay [40], and immu­ (FF), penicillin (PNC), streptomycin (SM), ampicillin (AMP), sulfadia­
nochemical technology [41] can be used for OTC with high specificity zine (SDI), azithromycin (AZI), enrofloxacin (ENR), cephalexin (CEF),
and high sensitivity detection. However, owing to the disadvantages of alanine (Ala), arginine (Arg), glutathione (GSH), cysteine (Cys), fructose
expensive instruments, cumbersome sample preparation procedures, (Fru), lactose (Lac), and cellulose ester dialysis membranes (500
high requirements, and high costs, it cannot available for point-of-care MWCO) were purchased from Yuanye Bio-Technology Co., Ltd.
testing [42]. Fluorometry is considered a more efficient approach (Shanghai, China). Tyrosine (Tyr) and lysine (Lys) were purchased from
owing to its simplicity and convenient operation, making it a better Solarbio Science & Technology Co., Ltd. (Beijing, China). Eu
choice for OTC monitoring; however, most single-emission probes are (NO3)3⋅6H2O, sucrose (Suc), ascorbic acid (AA), and glucose (Glu) were
prone to disturbance from detection background and environmental obtained from Macklin Reagent Co., Ltd. (Shanghai, China). Waters
factors. Adopting multiple signals is a potent solution to improve signal Oasis HLB cartridges were obtained from Waters Co., Ltd. (Massachu­
stability and achieve accurate and sensitive detection; thus, the ratio­ setts, United States). Britton Robinson (BR) buffer solutions ranging
metric FL method has been widely explored. Furthermore, ratiometric from pH 5.0 to 12.0 were used. All other chemicals used were of
sensors exhibit marked FL color gradients that are easily analyzed, analytical purity grade, and deionized water was utilized throughout the
making them more convenient for visualization than a single-color experiments.
readout, and provide insights for establishing this research method.

Scheme 1. Schematic diagram of OTC sensitivity and visual assisted detection based on the N-CQDs/Eu3+ ratio fluorescence sensor.

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2.2. Synthesis and optimization of N-CQDs 2.5. Selectivity evaluation

The N-CQDs were synthesized using a one-step hydrothermal The selectivity of the N-CQDs/Eu3+-based ratiometric FL sensor was
method with freeze-dried banana peel and DETA, following our previ­ evaluated by examining interfering substances typically found in pork
ously developed procedure with slight modifications [43]. Briefly, 0.85 samples, including antibiotics (TC, DOX, CTC, FF, PNC, SM, AMP, SDI,
g of banana peel powder, 300 μL of DETA, and 20 mL of deionized water AZI, ENR, and CEF), representative amino acids (Try, Lys, Cys, Ala, Arg,
were sequentially added to a Teflon-lined autoclave. The reaction GSH, AA, Glu, Fru, Lac, and Suc), and some inorganic ions (K+, Mg2+,
mixture was then subjected to 10 min ultrasonication to ensure thor­ Ca2+, Na+, Cl− , and CO2– 3 ). Three replicates were performed to ensure
ough mixing. Subsequently, the mixture was heated at 190 ◦ C for 12 h. the stability and reliability of the experimental results.
The Teflon-lined autoclave was naturally cooled, following which the
supernatant was collected with a 5 mL centrifuge tube. The collection 2.6. Smartphone-assisted N-CQDs/Eu3+-based ratiometric FL sensor for
solution was centrifuged at 10000 rpm for 10 min, and the resulting OTC visualization detection
brown-yellow product was filtered using a 0.22 µm filter membrane. The
purified solution was washed with dichloromethane and dialyzed The color changes of the established system were semi-quantitatively
against a dialysis membrane (500 MWCO) for 48 h to remove any excess analyzed using the Color Recognizer APP on a smartphone to detect
reactive material. Optimal conditions for obtaining higher FL intensity OTC. OTC at different concentrations and the N-CQDs/Eu3+ ratiometric
were determined through the optimization of banana peel powder FL probe solution were added into centrifuge tubes to prepare a total
dosage (0.55, 0.70, 0.85, 1.00, and 1.15 g), the DETA volume (100, 200, volume of 3 mL. The solution in each centrifuge tube was mixed using a
300, 400, 500, and 600 μL), reaction time (6, 8, 10, 12, and 14 h), and vortex mixer and transferred to 1.0 cm × 1.0 cm quartz cuvettes. Next,
reaction temperature (150, 160, 170, 180, 190, and 200 ◦ C). Taking the ratiometric FL sensing system images for the different OTC con­
quinine sulfate (dissolved in 0.1 M H2SO4 solution, Φst = 54%, ηst = centrations were captured using a smartphone under UV light at 365 nm.
1.33) as the standard sample [31], the following formula was used to The color images were converted using the Color Recognizer APP into
calculate the QY of the N-CQDs: digital values corresponding to the red (R) and blue (B) color channels,
and the red-blue ratio (R/B ratio) was determined using semi-
ΦN-CQDs = Φst(YN-CQDs/Yst)(Ast/AN-CQDs)(ηst/ηN-CQDs)2 (1)
quantitative calculations. For evaluation of the effect of freeze–thaw
where Φ, Y, A, and η represent the QY, integrated photoluminescence cycles and bench-top stability on the smartphone-assisted N-CQDs/
intensity, absorbance, and refractive index, respectively. Finally, the Eu3+-based ratiometric FL sensor, samples were prepared and stored at
purified N-CQDs solution was stored in a 4 ◦ C refrigerator for later use. − 20 ◦ C and 23 ◦ C, respectively, before being analyzed [35]. The
resulting concentrations were compared with the corresponding
additions.
2.3. Characterization of N-CQDs
2.7. Analysis of real samples
Ultraviolet–visible spectroscopy (UV–Vis) measurements were con­
ducted using a UV-2802H UV–Vis spectrophotometer (Uneco, China). Pork muscle and swine urine were used as real samples to validate
The FL spectra of N-CQDs were obtained using a Gangdong F-320 FL the practicability of the sensing platform [43]. An aliquot of 5 g (with an
spectrophotometer (Gangdong, China). Transmission electron micro­ accuracy of 0.01 g) of pork muscle and varying volumes of Na2EDTA-
scopy (TEM) observations were performed using a Tecnai G2 F30 mi­ Mclivainc butter (20 mL, 20 mL, and 10 mL, 0.1 M) were added to a 50
croscope with an acceleration voltage of 300 kV (Oregon, United States). mL polypropylene centrifuge tube, and subjected to ultrasonication for
Fourier transform infrared (FTIR) spectra were recorded using a Shi­ 10 min in ice water. This step was followed by centrifugation at 3000
madzu IRAFFinity-IS spectrometer (Tokyo, Japan). X-ray photoelectron rpm for 5 min (temperature below 15 ◦ C) for three repetitions. The su­
spectroscopy (XPS) measurements were performed using an ESCALAB pernatants were combined, and the volume was adjusted to 50 mL using
250Xi spectrometer (Massachusetts, United States). the Na2EDTA-Mclivainc butter solution. This was followed by centrifu­
gation at 5000 rpm for 10 min (temperature below 15 ◦ C). Finally, the
collected supernatant was purified using HLB solid-phase extraction and
2.4. Development and optimization of the N-CQDs/Eu3+-based stored at 4 ◦ C.
ratiometric FL sensor for OTC Swine urine was centrifuged at 8000 rpm for 20 min to remove
residue (temperature below 15 ◦ C). Then, the supernatant was filtered
The ratiometric FL probe (N-CQDs/Eu3+) for OTC detection was through a 0.22 µm filter membrane to remove impurities. Different
assembled as follows: in a test tube, 50 μL of diluted N-CQDs solution concentrations of OTC standard solution were added to each sample,
(300-fold) and 100 μL of Eu(NO3)3 solution (15 mg mL− 1) were added. and the FL emission spectrum was measured. All FL measurements were
Subsequently, 1 mL of OTC solution (0.01 μg mL− 1-25 μg mL− 1) and 400 performed three times in parallel.
μL BR buffer (pH = 10) were added. The mixture solution was supple­
mented to 3 mL with deionized water. The reaction system was incu­ 3. Results and discussion
bated at room temperature for 10 min. The intensity ratio of the N-
CQDs/Eu3+-based ratiometric FL sensor at 621 nm and 445 nm (F621/ 3.1. Synthesis and optimization of N-CQDs
F445) emission wavelengths was measured at 380 nm excitation wave­
length to quantitatively analyze OTC. The limit-of-detection (LOD) of N- Banana peel is an environmentally friendly, readily available, and
CQDs/Eu3+ for OTC detection was calculated using the formula: LOD = economical biowaste abundant in carbon, making it suitable for CQDs
3SB
S , where SB represents the standard error for 10 consecutive scans of synthesis. In this study, N-CQDs were synthesized using banana peel as a
the blank sample, and S is the slope of the calibration curve. The carbon source and DETA as a nitrogen source using a one-step hydro­
experimental conditions were optimized, including the concentration of thermal method [44,45]. As illustrated in Fig. S1, the synthesis condi­
Eu3+ (5, 10, 15, 20, and 25 mg mL− 1), volume of Eu3+ (25, 50, 75, 100, tions were optimized by evaluating the FL intensity. The dosage of
125, 150, and 175 μL), volume of BR buffer (100, 200, 300, 400, 500, banana peel powder was optimized within the range of 0.55 to 1.15 g,
and 600 μL), pH (5, 6, 7, 8, 9, 10, 11, and 12), and reaction time (0, 10, and the highest FL intensity (666.276 a.u.) was observed at 0.85 g
20, 30, 40, 50, and 60 min), to determine the optimal experimental (Fig. S1a). Similarly, a volume of 300 μL of DETA was selected, resulting
conditions for OTC detection. in a maximum FL intensity of 674.945 a.u. (Fig. S1b). The reaction time

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and temperature substantially affected the degree of carbonization. be 11.11%. Fan [51] and cooperator were also developed using Eu
Within the tested time range of 6 h to 14 h, the FL intensity of N-CQDs (NO3)3⋅6H2O, citric acid, and N, N ’-diethylthiourea to synthesize
peaked at 12 h (887.220 a.u.) (Fig.S1c). The reaction temperature of europium-doped carbon dots by one-step hydrothermal method to
190 ◦ C was chosen as the optimum, yielding an FL intensity of 2052.266 detect TCs. However, the raw material used in our procedure was more
a.u. (Fig. S1d). The FL intensity of N-CQDs gradually increased with economical and environmentally friendly than that used by them and
increasing reaction temperature, consistent with a previous study in possessed a high QY. In addition, to study the FL stability of N-CQDs, we
which higher temperature positively affected the carbonization and detected the change of FL intensity after storage at room temperature for
surface functionalization of N-CQDs [46]. Based on these results, the 30 days and under UV irradiation for 90 min. The results are shown in
following optimal parameters were selected: 0.85 g banana peel powder, Fig. S2, indicating that the synthesized N-CQDs were significantly
300 μL DETA, 12 h reaction time, temperature of 190 ◦ C. stable.
The particle morphology and size distribution of the as-synthesized
3.2. Characterization of N-CQDs N-CQDs were examined using high-resolution TEM. The images
revealed that the N-CQDs had a quasi-spherical shape and were well-
The optical characteristics of N-CQDs were illustrated using UV–Vis dispersed, displaying uniform dimensions. An inset image in Fig. 1c
absorption and FL spectra, as presented in Fig. 1a and b. First, the displays the ordered lattice fringes of the N-CQDs with a spacing of 0.25
diluted N-CQDs solution appeared as a colorless liquid under natural nm, which indicates excellent crystallization (Fig. 1c). These findings
light and exhibited a bright blue color under a UV lamp (365 nm). The were consistent with the particle morphology of N-CQDs synthesized
UV–Vis absorption spectrum revealed an absorption peak at 336 nm, using watermelon juice as the precursor by Lu et al. [52]. Moreover, the
which may be attributed to the n-π* electronic transition of C = O groups particle diameters of the N-CQDs were calculated; the average particle
[47]. The FL spectra of N-CQDs exhibited a slight red shift as the exci­ diameter was 3.02 nm, ranging from 1.15 to 5.93 nm (Fig. 1d).
tation wavelength varied from 340 to 390 nm, with an intense lumi­ The FTIR spectrum was utilized to characterize the surface functional
nescence observed at 445 nm when excited at 370 nm. Previous research groups of the N-CQDs; the results are presented in Fig. 2. The FTIR
has reported that various complicating factors, including aspects like spectrum of N-CQDs exhibited a broad peak centered at 3040 cm− 1,
size, surface defects, and surface passivation of CQDs, can significantly attributed to O-H/N-H and C-H groups’ stretching vibrations [53]. The
influence the electronic states and result in the red-shift phenomenon of characteristic peaks observed at 2937 cm− 1 and 2877 cm− 1 corre­
the FL spectrum [48,49]. In contrast, our study suggests that the sponded to the stretching vibration and bending vibration of methyl or
observed slight red-shift phenomenon may be primarily attributed to a methylene (C-H) groups [54]. The peak at 1632 cm− 1 could be attrib­
higher degree of surface passivation and less surface defects of CQDs. uted to C–– C absorption and –COOH stretching vibrations [55]. The
This finding is consistent with the work of Chawre, who prepared orange peaks at 1348 cm− 1 were assigned to the stretching vibration of C-N,
and red CQDs using p-phenylenediamine and tris(hydroxymethyl) confirming successful nitrogen doping in N-CQDs [56]. Additionally, the
aminomethane, respectively [50]. The QY of N-CQDs was measured to peaks at 1028 cm− 1 and 620 cm− 1 were attributed to C-O and N-H

Fig. 1. The optical characteristics of N-CQDs. (a) UV–Vis absorption (black line), fluorescence excitation (red line) and emission (blue line) spectra of N-CQDs. The
inset: image shows the photographs of N-CQDs under daylight (right) and under UV light of 365 nm (left). (b) Excitation-dependent fluorescence spectra of N-CQDs.
(c) TEM images of N-CQDs. The inset: the high-resolution TEM image of the N-CQDs. (d) The size distribution of N-CQDs.

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and O–– C bonds (Fig. 3d). These results indicate the presence of
graphitized carbon nuclei and the successful enrichment of hydrophilic
groups on the N-CQDs.

3.3. Development and optimization of the N-CQDs/Eu3+-based

ratiometric FL sensor

Based on the observation that the FL intensity of N-CQDs was

quenched and the FL intensity of Eu3+ was significantly increased upon
the addition of OTC, a ratiometric FL sensor based on N-CQDs/Eu3+ was
designed for OTC detection. The optimal excitation wavelength of N-
CQDs was 370 nm and that of Eu3+ was 400 nm (Fig. S3). Considering
these excitation wavelengths, 380 nm was selected as the optimum
excitation wavelength for the ratiometric FL probe. The intensity ratio of
F621/F445 was calculated for optimal performance during OTC detection.
Several important parameters of the ratiometric FL probe were investi­
gated, including the concentration of N-CQDs, the amount and volume
of Eu3+, the buffer composition, and the reaction time. As illustrated in
Fig. S4a, the optimal condition was obtained when the N-CQDs were
Fig. 2. The FTIR spectrum of the N-CQDs.
diluted 30-fold. As illustrated in Fig. S4b and c, the optimal amount and
volume of Eu3+ were 15 mg mL− 1 and 100 μL, respectively. The optimal
functional groups on N-CQDs, respectively [57]. The surface of N-CQDs pH of the BR buffer was found to be 10 (Fig. S4d), possibly owing to the
exhibited unsaturated carbonaceous structures, oxygenated groups, and surface protonation process of N-CQDs under alkaline conditions. This
nitrogen groups, enhancing their hydrophilicity. process enhances the coordination capacity of the loop structure,
Furthermore, XPS spectroscopy was used to analyze the elemental thereby increasing the generation of Eu3+ red emission [58]. Moving
compositions and chemical bonds of N-CQDs, as illustrated in Fig. 3. The forward, the F621/F445 ratio exhibited its highest value with an optimal
full-range XPS spectrum exhibited three peaks at 284.84, 399.55, and volume of 400 μL for the BR buffer (Fig. S4e). Fig. S4f illustrated that the
531.24 eV, corresponding to carbon (C1s), nitrogen (N1s), and oxygen response time did not substantially influence the F621/F445 ratio;
(O1s), respectively (Fig. 3a). The mass fraction ratios of C, N, and O were therefore, a 10-min response time was selected for OTC detection. In
calculated as 78.09%, 14.47%, and 7.44%, respectively. The high- general, N-CQDs diluted 30-fold (50 μL), 100 μL Eu3+ (15 mg mL− 1),
resolution XPS spectrum of C1s (Fig. 3b) could be fitted into four 400 μL BR buffer (pH = 10), and a 10 min response time were chosen for
peaks located at 284.77, 285.44, 286.29, and 287.93 eV, linked to C–C, this study.
C–N, C–O, and C– – O, respectively. The N1s spectrum exhibited three
peaks at 399.34, 400.27, and 401.49 eV, corresponding to C– – N–C, N–
3.4. Sensitivity of the N-CQDs/Eu3+-based ratiometric FL sensor for OTC
(C)3, and N-H bonds, respectively (Fig. 3c). Two peaks centered at
531.13 eV and 533.58 eV in the O1s spectrum were attributed to O–C Based on the optimal conditions, a ratiometric FL sensor based on N-

Fig. 3. XPS spectrum of N-CQDs. (a) Complete XPS survey spectrum, high-resolution XPS spectra of (b) C1s, (c) N1s, and (d) O1s.

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CQDs/Eu3+ was developed for OTC detection. As illustrated in Fig. 4a, Eu3+-OTC compound had a low emission peak (purple curve). In addi­
the F621/F445 ratio gradually increased with increasing OTC concen­ tion, the FL intensity of N-CQDs at 445 nm was quenched, while the FL
tration. The results revealed two distinct linear relationships with OTC intensity of Eu3+ at 596 nm and 621 nm markedly increased after
concentrations from 0.01 to 5 μg mL− 1 (R2 = 0.9963) and from 5 to 25 introducing OTC (green curve). The emission peak at 621 nm, which had
μg mL− 1 (R2 = 0.9979) (Fig. 4b). Moreover, the LOD was calculated to a more distinct response to OTC, was used as the FL signal for Eu3+.
be 4.9 ng mL− 1 (3σ). The LOD was lower than the permissible OTC Thus, the reverse change of the two FL signals, N-CQDs, and Eu3+,
concentration (15 μg kg− 1) for immunoassay detection in pork muscle, provided a prerequisite for the N-CQDs/Eu3+-based ratiometric FL
as stated in Bulletin No. 1025-20-2008 from the Ministry of Agriculture, sensor. The response mechanism of the N-CQDs/Eu3+-based ratiometric
demonstrating that the N-CQDs/Eu3+-based ratiometric FL sensor was FL sensor for OTC testing was evaluated in detail using optimal condi­
more sensitive for OTC detection. Compared with the method by He tions. To explain the OTC-induced quenching mechanism of N-CQDs, the
et al., in which a LOD of 0.118 μM was obtained for OTC using a UV–Vis absorption spectrum of OTC was compared with the excitation
luminescent europium metal–organic framework, the current N-CQDs/ spectra of N-CQDs. Partial overlap was present between the excitation
Eu3+-based ratiometric FL sensor exhibited improved sensitivity [59]. spectra of N-CQDs and the absorption spectra of OTC at 354 nm, sug­
gesting that the inner filter effect (IFE) existed between OTC and N-
CQDs [60]. Furthermore, the FL lifetime of N-CQDs was almost un­
3.5. Selectivity of the N-CQDs/Eu3+-based ratiometric FL sensor
changed from 11.21 to 10.17 ns after introducing OTC (Fig. 6b),
revealing that no energy transfer process or dynamic quenching effect
To further elucidate the selectivity of the N-CQDs/Eu3+-based
was present between N-CQDs and OTC [61]. This result was consistent
ratiometric FL sensor, the influence of other antibiotics (TC, DOX, CTC,
with the results of Pan et al., which revealed IFE as the major quenching
FF, PNC, SM, SDI, AZI, AMP, ENR, and CEF) and a series of possible
mechanism [62]. The UV–Vis absorption spectra are illustrated in
coexisting substances (Try, Lys, Cys, Ala, Ary, GSH, AA, Glu, Fru, Lac,
Fig. 6c. The N-CQDs had no substantial influence on the absorption and
Suc, K+, Fe3+, Mg2+, Ca2+, Na+, Cl− , and CO2– 3 ) were investigated. As
optical properties of Eu3+, and the results revealed that N-CQDs did not
presented in Fig. 5a and b, obvious signal changes in the F621/F445 ratio
influence the characteristic FL of Eu3+ [63]. OTC effectively increased
were only observed for tetracyclines antibiotics (TC, CTC, and DOX),
the FL at 621 nm owing to the specific chelation between OTC and Eu3+
which have similar chemical structures and functional groups to OTC.
mediated by the β-diketonate configuration, acting as an “antenna” [29]
The results demonstrated that the N-CQDs/Eu3+-based ratiometric FL
accompanied by the energy transfer Eu3+ caused by the antenna effect
sensor had excellent selectivity for detecting tetracyclines antibiotics.
(AE) [64]. As depicted in Fig. 6d, the N-CQDs + Eu3++OTC emission
peak exhibited a noticeable red shift and an enhanced absorption in­
3.6. Mechanism of the N-CQDs/Eu3+-based ratiometric FL sensor for tensity compared with OTC, indicating the chelation of OTC with Eu3+
OTC [19]. This was consistent with the result of Chen et al., where the
emission peak increased at 596 nm (5D0→7F1) and 621 nm (5D0→7F2)
We performed additional experiments to validate the feasibility of after the addition of OTC to N-CQDs/Eu3+ due to the characteristic
using the N-CQDs/Eu3+-based ratiometric FL sensor for OTC detection. transition of Eu3+ [65].
As presented in Fig. 6a, the FL intensity of N-CQDs coincided with N-
CQDs/Eu3+ (red curve), indicating that the incorporation of Eu3+ had a
negligible effect on the FL intensity of N-CQDs. The FL intensity of the

Fig. 4. Sensitivity of the N-CQDs/Eu3+-based ratiometric fluorescence sensor for OTC. (a) The changes of the N-CQDs/Eu3+ ratio fluorescence probe at 621 nm and
445 nm upon the addition of different concentrations of OTC from 0 to 25 μg mL− 1. (b) The linear relationships between F621/F445 and the concentration of OTC. (c)
The emission spectra of the N-CQDs/Eu3+-based ratiometric fluorescence sensor with the addition of OTC.

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Fig. 5. The N-CQDs/Eu3+-based ratiometric fluorescence sensor for selective responses to antibiotics (a and b) and possible coexisting substances (c and d) with or
without OTC.

Fig. 6. Mechanism of the OTC detection by the N-

CQDs/Eu3+-based ratiometric fluorescence sensor. (a)
Fluorescence spectra of N-CQDs (black line), N-CQDs
+ Eu3+ (red line), N-CQDs + OTC (blue line),
Eu3++OTC (purple line), and N-CQDs + Eu3++OTC
(green line). The inset: image shows the correspond­
ing fluorescent photographs under a 365 nm UV lamp.
(b) Transient fluorescence spectra of N-CQDs and N-
CQDs/Eu3+ at 380 nm in the absence and presence of
OTC. Conditions: N-CQDs: diluted 30-fold, Eu3+:15
mg mL− 1, OTC: 200.0 μg mL− 1. (c) UV–Vis spectra of
OTC (black) and excitation (red) and emission (blue)
spectra of N-CQDs. (d) The UV–Vis absorption spectra
of OTC, N-CQDs + Eu3+ and N-CQDs + Eu3++OTC.

3.7. Smartphone-assisted N-CQDs/Eu3+-based ratiometric FL sensor for exhibited successive color changes from blue to purple under a 365 nm
OTC visualization detection UV lamp (Fig. 7b). This observation was further verified using the
Commission Internationale de l’Eclairage’s (CIE) color coordinate dia­
In this study, the N-CQDs/Eu3+-based ratiometric FL sensor gram (Fig. 7a) and achieved similar results. Therefore, we proposed OTC

7
C. Wu et al. Microchemical Journal 194 (2023) 109283

Fig. 7. Smartphone-assisted N-CQDs/Eu3+ -based ratiometric fluorescence sensor for OTC visualization detection. (a) Chromaticity diagram of CIE in the presence of
different concentrations of OTC. (b) Linear relationship between color change (R/B ratio) and OTC concentrations. The inset: fluorescence photographs of the N-
CQDs/Eu3+-based ratiometric fluorescence sensor upon the addition of different concentrations of OTC under UV lamp irradiation at 365 nm.

detection using a mobile phone color reading and analysis function [66]. according to the guidelines established by the FDA [67]. The stability
A portable, easy, and economical smartphone-assisted N-CQDs/Eu3+- data indicate that the method remains relatively stable for a short
based ratiometric FL sensor was designed by integrating a smartphone duration at both − 20 ◦ C and 23 ◦ C (Table 2). Consequently, the method
application, Color Recognizer APP, as a signal reader and analyzer to can be effectively applied to samples stored at room temperature or kept
achieve on-site and real-time semi-quantitative OTC detection. The frozen for short periods.
images were obtained using the smartphone camera. Through analysis, These results indicated that the established method was promising
the semi-quantitative calculation of the R/B ratio was used to obtain the for on-site and real-time quantitative OTC detection in animal-derived
concentration of OTC in the samples. With increasing OTC concentra­ foods. In recent years, other sensors have been developed to detect
tion, the percentage of R progressively increased while the proportion of OTC using CQDs as detection elements, which we have compared in
B gradually weakened. As presented in Fig. 7b, a linear relationship was Table S1. We found that our innovative method achieved a comparable
observed between the R/B ratio and diverse concentrations of OTC in or better LOD and visual linear range of OTC than other methods. Thus,
the range of 0.7–20 μg mL− 1 (R2 = 0.9955). Consequently, we propose we have developed an economical and environmentally friendly FL
using this method based on the N-CQDs/Eu3+-based ratiometric FL sensor using banana peel waste as raw material, which can reliably
sensor for convenient field and visual OTC detection. detect OTC residues in pork samples.

4. Conclusions
3.8. Smartphone-assisted N-CQDs/Eu3+-based ratiometric FL sensor for
OTC detection in pork samples
The N-CQDs/Eu3+-based ratiometric FL sensor was developed as a
novel rapid, and selective method for OTC detection. N-CQDs with good
The developed smartphone-assisted N-CQDs/Eu3+-based ratiometric
water solubility, prominent FL, and favorable stability were synthesized
FL sensor was applied to detect OTC in pork samples. As presented in
via a one-step hydrothermal method employing banana peel and DETA
Table 1, the smartphone-based N-CQDs/Eu3+-based ratiometric FL
as precursors. The complexes formed by N-CQDs and Eu3+ were stable
sensor achieved good OTC detection results (96.89–103.20%) and
and effectively overcame the interference of external environmental
reasonable relative standard deviation (RSD) (0.20–1.68%). The
factors. The N-CQDs/Eu3+-based ratiometric FL sensor exhibited a good
intraday and interday repeatability of the testing system was evaluated

Table 1
Measurements of OTC spiked in real samples using the development smartphone-assisted N-CQDs/Eu3+-based ratiometric fluorescence sensor.
Samples Added (μg Founded (μg Figures Recovery RSD Intraday precision Interday precision Intraday accuracy Interday accuracy
mL− 1) mL− 1) (%) (%) (RSD%) (RSD%) recovery (%) recovery (%)

Pork 3 3.01 ± 0.05 100.34 1.68 2.46 2.56 99.88 100.71

muscle

5 5.16 ± 0.05 103.20 1.14 6.79 6.80 104.78 104.90

15 14.53 ± 0.23 96.89 1.64 4.28 7.99 96.26 92.57

Swine 3 2.96 ± 0.03 98.67 1.11 1.49 1.46 99.41 98.67

urine

5 4.91 ± 0.04 98.20 1.02 2.25 6.50 104.23 101.15

15 14.90 ± 0.03 99.33 0.20 4.39 4.54 101.16 97.98

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C. Wu et al. Microchemical Journal 194 (2023) 109283

Table 2
Details of the stability of the proposed method for three concentrations investigated.
Samples Added (μg mL− 1) Freeze-thaw cycles (3 d) Bench-top stability (24 h)
− 1
Founded (μg mL ) RSD (%) Recovery (%) Founded (μg mL− 1) RSD (%) Recovery (%)

Pork muscle 3 2.82 ± 0.15 5.26 94.14 2.73 ± 0.14 5.37 91.12
5 4.73 ± 0.12 2.62 94.65 4.45 ± 0.23 5.29 89.03
15 14.91 ± 0.17 1.12 99.40 14.96 ± 0.21 1.45 99.76
Swine urine 3 3.13 ± 0.04 1.14 104.43 3.05 ± 0.10 3.44 101.58
5 5.02 ± 0.03 0.68 100.42 4.69 ± 0.20 4.26 93.85
15 13.83 ± 0.15 1.10 92.20 13.78 ± 0.44 3.20 91.87

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