Nitrogen-Doped Durian Shell Derived Carbon Dots for Inner Filter Effect Mediated Sensing of Tetracycline and Fluorescent Ink.

Photoluminescent carbon dots have gained increasing attention in recent years due to their unique optical properties. Herein, a facile one-pot hydrothermal process is used to develop nitrogen-doped carbon dots (NCDs) with durian shell waste as the precursor and Tris base as the doping agent. The synthesized NCDs showed a quantum yield of 12.93% with a blue fluorescence under UV-light irradiation and maximum emission at 414 nm at an excitation wavelength of 340 nm. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy showed the presence of nitrogen and oxygen functional groups on the NCD surface. The particles were quasi-spherical with an average particle diameter of 6.5 nm. The synthesized NCDs were resistant to photobleaching and stable under a wide range of pH but were negatively affected by increasing temperature. NCDs showed high selectivity to Tetracycline as the fluorescence of NCDs was quenched significantly by Tetracycline as a result of the inner filter effect. Based on sensitivity experiments, a linear relationship (R2 = 0.989) was developed over a concentration range of 0-30 µM with a detection limit of 75 nM (S/N = 3). The linear model was validated with two water samples (lake water and tap water) with relative recoveries of 98.6-108.5% and an RSD of <3.5%.

Highly efficient and sensitive detection of tetracycline in environmental water: Insights into the synergistic mechanism of biomass-derived carbon dots and N-methyl pyrrolidone solvent.

The tetracycline (TC) residue in water environment has caused serious public safety issue. Thus, efficient sensing of TC is highly desirable for environmental protection. Herein, biomass-derived nitrogen-doped carbon dots (N-CDs) synthesized from natural Ophiopogon japonicus f. nanus (O. japonicus) were used for TC detection. The unique solvent synergism efficiently enhanced detection sensitivity, and the detailed sensing mechanism was deeply investigated. The blue fluorescence of N-CDs was quenched by TC via static quenching and inner filter effect. Moreover, the enhancement of green fluorescence from deprotonated TC was firstly proposed and sufficiently verified. The solvent effect of N-methyl pyrrolidone (NMP) and the fluorescence resonance energy transfer (FRET) with N-CDs achieved an instantaneous enhancement of the green emission by 64-fold. Accordingly, a ratiometric fluorescence method was constructed for rapid and sensitive sensing of TC with a low detection limit of 6.3 nM within 60 s. The synergistic effect of N-CDs and solvent assistance significantly improved the sensitivity by 7-fold compared to that in water. Remarkably, the biomass-derived N-CDs displayed low cost, good solubility, and desired stability. The deep insights into the synergism with solvent can provide prospects for the utilization of biomass-based materials and broaden the development of advanced sensors with promising applications.

Synthesis of N-doped and P-doped silicon quantum dots and their applications for tetracycline detection in the honey samples and antibacterial properties.

The abuse of tetracycline can lead to its residue in animal derived foods, posing many potential hazards to human health. Therefore, rapid and accurate detection of tetracycline is an important means to ensure food safety. Nitrogen doped and phosphorus doped silicon quantum dots (N-SiQDs, P-SiQDs) with remarkable optical stability were fabricated via a one-pot hydrothermal procedure in this study. Upon the excitation at 346 nm, N-SiQDs and P-SiQDs emitted fluorescence at 431 nm and 505 nm, respectively. Two SiQDs had the potential to serve as a probe for detecting low concentrations of tetracycline (TC), employing a mechanism of the static quenching effect. The calibration curves of N-SiQDs and P-SiQDs were linear within the range of 0-0.8 µM and 0-0.4 µM, the limits of detection were low as 5.35 × 10-4 µmol/L and 6.90 × 10-3 µmol/L, respectively. This method could be used successfully to detect TC in honey samples. Moreover, the remarkable antibacterial efficacy of two SiQDs could be attributed to the generation of a large number of intracellular reactive oxygen species. The SEM images showed that the structure of bacterial cell was disrupted and the surface became irregular when treated with both SiQDs. These properties enabled potential usage of SiQDs as excellent antibacterial material for different biomedical applications.

A self-calibrating ratiometric fluorescence sensor with photonic crystal-based signal amplification for the detection of tetracycline in food.

A dual-color ratiometric fluorescence sensor based on photonic crystals (PCs) was developed to detect tetracycline (TC) in food. PC was fabricated via self-assembly of carbon dots (CDs)-loaded SiO2 nanoparticles. Gold nanoclusters (AuNCs) and copper ions (Cu2+) were then adsorbed onto the PC for sensor fabrication. The fluorescence of AuNCs was amplified by the PC with an enhancement ratio of 7.6, providing higher sensitivity. The fluorescence of AuNCs was quenched by Cu2+, whereas that of CDs remained unchanged as an internal reference. TC restored the fluorescence of AuNCs owing to its complexation with Cu2+, resulting in a change in the fluorescence intensity ratio. The sensor exhibited a good linear relationship with TC concentrations ranging from 0.1 to 10 µM, with a detection limit of 34 nM. Furthermore, the sensor was applied for TC detection in food with satisfactory recoveries and relative standard deviations, revealing great potential in practical application.

New method for morphological identification and simultaneous quantification of multiple tetracyclines by a white fluorescent probe.

The threat of tetracycline antibiotics to the environment and human health is attracting widespread attention. The development of morphological analysis and quantitative techniques of multiple tetracyclines is of great significance for the evaluation of biochemical toxicity, wide-spectrum antibacterial property and degradation cycle between different tetracyclines. In this study, the white fluorescent Eu/Tb@CDs was synthesized and applied successfully to the identification and detection of the most widely used tetracycline antibiotics (tetracycline (TC), oxytetracycline (OC), chlortetracycline (CC) and doxycycline (DC)) with detection limits all below 1 nM. For the actual water samples with coexistence of the above 4 tetracyclines, their simultaneous morphology identification and accurate quantitative detection can also be realized through simple spectrometric measurement. In addition, the selective and competitive experiments have been carried out on the pollutants widely present in water, and the results have also confirmed that other pollutants could not interfere with the detection of the above 4 tetracyclines. It is undeniable that this work will conveniently and visually reveal the existence information and geographical distribution characteristics of different tetracycline antibiotics in the environment and their action mechanism on organisms.

A wearable gloved sensor based on fluorescent Ag nanoparticles and europium complexes for visualized assessment of tetracycline in food samples.

The abuse of tetracycline antibiotics leads to accumulating residues in the human body, seriously affecting human health. Establishing a sensitive, efficient, and reliable method for qualitative and quantitative detection of tetracycline (TC) is necessary. This study integrated silver nanoclusters and europium-based materials into the same nano-detection system to construct a visual and rapid TC sensor with rich fluorescence color changes. The nanosensor has the advantages of a low detection limit (10.5 nM), high detection sensitivity, fast response, and wide linear range (0-30 µM), which can meet the analysis requirements of different types of food samples. In addition, portable devices based on paper and gloves were designed. Through the smartphone's chromaticity acquisition and calculation analysis application (APP), the real-time rapid visual intelligent analysis of TC in the sample can be realized, which guides the intelligent application of multicolor fluorescent nanosensors.

A Zn-coordination polymer for the quantitative and selective colorimetric detection of residual tetracycline in aqueous solution and urine.

A one-step solvothermal synthesis provides a functional crystalline one-dimensional Zn-coordination polymer (Zn-CP) with excellent stability in aqueous solution over a wide range of temperature and pH. Zn-CP is a rapid, highly sensitive and selective sensor for detecting tetracycline (TC). Quantitative TC detection is based on the ratio of fluorescence intensities I530/I420, with a limit of detection (LOD) of 5.51 nM in aqueous solution and 47.17 nM in human urine. The characteristics of colorimetric TC sensing by Zn-CP are highly favorable for application because the color of Zn-CP changes in the visible part of the spectrum from blue-purple to yellow-green upon addition of TC. Conversion of these colors into an RGB signal is simply achieved with an app for the smart phone and provides LODs of 8.04 nM and 0.13 µM TC in water and urine, respectively. Our suggested sensing mechanisms assume that the fluorescence intensity of Zn-CP@TC at 530 nm is enhanced by energy transfer of Zn-CP to TC, while the fluorescence of Zn-CP at 420 nm is quenched by photoinduced electron transfer (PET) from TC to the organic ligand in Zn-CP. These fluorescence properties make Zn-CP a convenient, low-cost, rapid and green detection device for monitoring TC under physiological conditions and in aqueous media.

Alkali-Etched Imprinted Mn-Based Prussian Blue Analogues with Superior Oxidase-Mimetic Activity and Precise Recognition for Tetracycline Colorimetric Sensing.

As a typical antibiotic pollutant, tetracycline (TC) is producing increasing threats to the ecosystem and human health, and exploring convenient means for monitoring of TC is needed. Here, we proposed alkali-etched imprinted Mn-based Prussian blue analogues featuring superior oxidase-mimetic activity and precise recognition for the colorimetric sensing of TC. Simply etching Mn-based Prussian blue analogues (Mn-PBAs) with NaOH could expose the sites and surfaces to significantly improve their catalytic activity. Density functional theory calculations were employed to screen the molecularly imprinted polymer (MIP) layer for target identification. Consequently, the designed Mn-PBANaOH@MIP possessed the rich channels for substrates to get in touch with the active Mn-PBANaOH core, showing an excellent catalytic capacity to trigger the chromogenic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) without the use of H2O2. If TC was introduced, it would be recognized selectively by the MIP shell and masked the channels for TMB access, resulting in the obstruction of the chromogenic reaction. According to this mechanism, selective optical detection of TC was achieved, and performance stability, reusability, and reliability as well as practicability were also verified, promising potential for TC monitoring in complex matrices. Our work not only presents an effective way to enhance the enzyme-like activity of Prussian blue analogues but also provides a facile approach for TC sensing. Additionally, the work will inspire the exploration of molecularly imprinted nanozymes for various applications.

A Sensitive Fluorescence Sensor for Tetracycline Determination Based on Adenine Thymine-Rich Single-Stranded DNA-Templated Copper Nanoclusters.

A sensitive fluorescent sensor has been developed for the determination of tetracycline (TC) using adenine thymine (AT)-rich single-stranded DNA (ssDNA) templated copper nanoclusters (CuNCs) as a fluorescent probe. Fluorescent ssDNA-CuNCs were synthesized by employing AT-rich ssDNA as templates and ascorbic acid as reducing agents through a facile one-step method. The as-prepared ssDNA-CuNCs exhibited strong fluorescence with a large Stokes shift (240 nm) and stable fluorescence emission. In the presence of TC, the fluorescent intensity of ssDNA-CuNCs was obviously decreased through the inner filter effect, due to the spectral overlapping between ssDNA-CuNCs and TC. Under the optimal conditions, the strategy exhibited sensitive detection of TC with a linear range from 2 nM to 30 µM and with a limit of detection of 0.5 nM. Furthermore, the sensor was successfully applied for the detection of TC in milk samples. Therefore, it provided a simple, rapid, and label-free fluorescent method for TC detection.

Photoelectrochemical aptasensor for sensitive detection of tetracycline in soil based on CdTe-BiOBr heterojunction: Improved photoactivity enabled by Z-scheme electron transfer pathway.

Exploring effective methods for tetracycline (TC) detection in soil has great significance because of its emerging environmental problem and increasing threat to soil quality and general public health worldwide. In this work, a sensitive photoelectrochemical (PEC) aptasensor toward TC detection was designed and constructed based on an efficient photosensitive material of Z-scheme CdTe-BiOBr heterojunction. Due to the sensitization of CdTe quantum dots (QDs) on the BiOBr nanoflowers, the photocurrent intensity of the CdTe-BiOBr heterojunction was enhanced about 5.0-fold and 8.0-fold than that of pure BiOBr and CdTe under visible-light irradiation, which was attributed to the low electron-hole combination efficiency, high visible light utilization efficiency, and high carrier density of the heterojunction. On the merits of the excellent PEC activity of the CdTe-BiOBr and the specificity of the aptamer, the proposed PEC aptasensor has the advantages of satisfying linear range (from 10 to 1500 pM), low detection limit (9.25 pM), good selectivity, and reproducibility. In addition, acceptable accuracy was obtained for TC detection in real soil sample, giving acceptable accuracy in comparison with the referenced high-performance liquid chromatography-diode array detector method, revealing a promising avenue for accurate and ultrasensitive estimation of other kinds of contaminants in the broad field of analysis.

Fluorescent and colorimetric dual-mode detection of tetracycline in wastewater based on heteroatoms-doped reduced state carbon dots.

A large amount of tetracycline (TC) persists in water, soil, food, and feed due to the overuse of antibiotics, causing serious environmental problems such as damage to ecosystems and posing risks to human health. Thus, there is an urgent need to find a method to detect TC that is practical, rapid, sensitive, and offers ready visualization of TC levels so that adequate remediation measures can be immediately implemented. Herein, we report a fluorescent and colorimetric dual-mode nanosensor for the detection of TC based on reduced state carbon dots (r-CDs). In the presence of TC, the emission fluorescence of r-CDs was quenched by the Förster resonance energy transfer mechanism to achieve high-sensitivity detection of TC with a low limit of detection (LOD) of 1.73 nM. Moreover, TC was also detected by r-CDs via a noticeable color change of the solution (from colorless to red) with the naked eye, having an LOD of 0.46 µM. Furthermore, r-CDs have excellent selectivity and sensitivity in detecting TC in wastewater, and therefore, have practical applications in wastewater treatment. The fluorescent and colorimetric dual-mode proposed in this work may offer a unique idea for the detection of TC, with great prospects for environmental wastewater applications.

Detection of Tetracycline in Water Using Glutathione-protected Fluorescent Gold Nanoclusters.

Tetracycline (Tc), a widely used antibiotic, is one of the major pollutants in water. Herein, glutathione (GSH)-protected Au nanoclusters (GSH-AuNCs) were prepared to detect Tc. The fluorescence quenching ratio of GSH-AuNCs shows an excellent linear response against tetracycline in the concentration range of 50 µg/L - 50 mg/L with the detection limit of 5.31 µg/L. For the test paper prepared by GSH-AuNCs, 1 mg/L Tc caused a significant difference that could be recognized by the naked eye. The method exhibited good selectivity and excellent recovery when applied to a tap water sample. The method has the potential for Tc detection in real samples.