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Detecting ammonia nitrogen in water using fluorescence with nitrogen-doped graphene quantum dots
Transactions of the Chinese Society of Agricultural Engineering 2025, 41(2): 242-250
Published: 30 January 2025
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Ammonia nitrogen (NH3-N) can serve as one of the key indicators of water quality. However, the NH3-N level can rapidly increase over a short period in intensive aquaculture, due to farming density, feeding modes, and water renewal frequency. The high-level NH3-N-induced stress can cause eutrophication damage to aquatic animals and even mortality. Therefore, it is crucial to detect the NH3-N in water, in order to prevent water quality deterioration for the safety of aquatic life. Particularly, the current detection of NH3-N is often complex, costly, time-consuming, and limited in detection range. This study aims to propose an accurate and rapid detection of high NH3-N concentrations in water. A nitrogen-doped graphene quantum dots (N-GQDs) fluorescent probe was then constructed to detect the NH3-N content in water. Firstly, the morphology and size distribution of the N-GQDs were examined using transmission electron microscopy (TEM). The lattice spacing of the N-GQDs was observed to be 0.20 nm, corresponding to the (100) lattice plane of the graphite structure. X-ray diffraction (XRD) analysis showed the diffraction peaks at 19° and 29° were attributed to the (101) and (002) crystal planes of graphene, respectively. Fourier transform infrared spectroscopy (FT-IR) analysis demonstrated the presence of carboxyl groups (-COOH) on the surface of the N-GQDs. The N1s spectrum of X-ray photoelectron spectroscopy (XPS) indicated that the nitrogen was doped in the GQDs in the form of pyrrole nitrogen. The characterization results from TEM, FT-IR, XPS, and XRD confirmed that the N-GQDs with a graphene crystal structure were successfully synthesized. Additionally, the optical properties were performed on the N-GQDs fluorescent probe. Specifically, the N-GQDs exhibited an absorption peak at 320 nm in the UV-Vis spectrum, due to the π→π* transition within the C=C structure. Meanwhile, the fluorescence spectra showed that the optimum excitation and emission wavelengths of the N-GQDs were 350 and 450 nm, respectively. The aqueous solution of N-GQDs shared a pale yellow under daylight and then emitted blue fluorescence under a 360 nm UV lamp. The N-GQDs fluorescent probe showed a good linear response (R2=0.99) to NH3-N concentration in the range of 0-9.0 mmol/L under the optimal experimental conditions (pH=7, N-GQDs concentration 0.8 mg/mL), with the detection limit concentration of 43.8 µmol/L and response time of 2 min. Furthermore, the stability, repeatability, and anti-interference properties of the fluorescent probe were carried out. The probe exhibited the excellent stability, and anti-interference properties against Na+, Hg+, Ag+, K+, Pb2+, Ca2+, Cd2+, and Cu2+. The fluorescence intensity of the probe still recovered to 77% of the initial value after three uses, indicating that the probe has good reproducibility. The response mechanism of the N-GQDs fluorescent probe to NH3-N was analyzed by UV-Vis, FT-IR, and fluorescence lifetime decay analysis and Stern-Volmmer equation. The carboxyl groups on the surface of the N-GQDs exhibited electron-accepting properties. The pyrrole nitrogen doped into the GQDs carried a slight positive charge. Ammonia acted as a typical electron donor, due to the lone pair of electrons on the nitrogen atom. Therefore, it inferred that the photo-induced electron transfer occurred between ammonia and the N-GQDs, resulting in the dynamic quenching of N-GQDs fluorescence. Finally, the N-GQDs fluorescent probe was used to determine the NH3-N in drinking, tap, and aquaculture water, with the recoveries of the spiked assay ranging from 75.03% to 128.16% and relative standard deviations (RSD) (n=3) lower than 13.53%. Consequently, the N-GQDs fluorescent probe also shared the potential applications in the detection of NH3-N in water.

Open Access Issue
Determination of Copper Ion in Drinking Water Using Poly(vinyl alcohol)/3-Mercaptopropionic Acid-Capped InP/ZnS Quantum Dots Fluorescent Film
Food Science 2024, 45(14): 227-233
Published: 25 July 2024
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PVA/MPA-InP/ZnS QD fluorescent film for rapid detection of trace Cu2+ was developed using 3-mercaptopropionic acid (MPA)-capped InP/ZnS quantum dots (MPA-InP/ZnS QDs) as the fluorescence-sensitive material and polyvinyl alcohol (PVA) as the substrate. The microstructure, optical properties and mechanical properties of the fluorescent film were characterized. The results showed that PVA interacted with MPA-InP/ZnS QDs through hydrogen bonds. The fluorescence intensity of the film was significantly correlated with Cu2+ concentration in the range of 0–1000 nmol/L (R2 = 0.95). The limit of detection (LOD) for Cu2+ was 23 nmol/L, and the response time was 6 minutes. Finally, the film was applied to the detection of trace Cu2+ in drinking water, beverages and alcoholic drinks with the advantages of high selectivity, rapid response and good portability, which exhibited a broad application prospect.

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