CN112920797B - N, S-doped water-soluble carbon quantum dot and application thereof - Google Patents
N, S-doped water-soluble carbon quantum dot and application thereof Download PDFInfo
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Abstract
The invention provides an N, S-doped water-soluble carbon quantum dot and application thereof, wherein the N, S-doped water-soluble carbon quantum dot takes purple garlic with rich alliin as a novel biomass carbon source, and the N, S-doped water-soluble carbon quantum dot is prepared by a one-step hydrothermal method; the N and S doped water-soluble carbon quantum has a fluorescence quenching effect on tetracycline, can detect the tetracycline by taking the carbon quantum dots as a fluorescent probe, has good selectivity and anti-interference performance, and provides more choices for the detection of the tetracycline.
Description
Technical Field
The invention relates to a quantum dot, in particular to an N and S doped water-soluble carbon quantum dot, and also relates to an application of the quantum dot, belonging to the technical field of novel carbon nano materials.
Background
The carbon quantum dot is a novel zero-dimensional nano material with carbon as a framework structure, and the particle size is less than 10 nm. Due to the size effect and quantum confinement effect generated by the extremely small particle size of the carbon quantum dots, the carbon quantum dots have good fluorescence stability and photobleaching resistance. Meanwhile, the carbon quantum dots also have excellent performances of high water solubility, high chemical stability, low cytotoxicity, good biocompatibility and the like, so that the carbon quantum dots not only have wide application value in the field of luminescent devices, but also are more suitable for being applied to the fields of biomedicine, biomarkers, cell imaging, biosensing and the like compared with the traditional semiconductor quantum dots. Currently, there are few studies on drug analysis and measurement using the fluorescence properties of carbon quantum dots.
Garlic is a common food beneficial to human bodies, and allicin, which is an active ingredient in garlic, is generated by catalyzing alliin through allinase, namely the alliin is a precursor of allicin.
Tetracycline is a broad-spectrum antibiotic produced or semi-synthesized by actinomycetes, has a bactericidal effect at a high concentration, and has a good inhibitory effect on various gram-negative bacteria, gram-positive bacteria, chlamydia, mycoplasma, rickettsia and the like. As the tetracycline has the advantages of wide antibacterial spectrum, low price and the like, the tetracycline is widely used in animal husbandry as a veterinary drug for preventing and treating various infectious diseases or as a feed additive for promoting the growth of livestock and poultry. However, studies show that tetracycline is easily remained in livestock and poultry bodies, and further harms human health through a food chain. Therefore, the tetracycline content in the product must be strictly controlled and regulated in various industries, and the conventional detection methods for tetracycline are microbiological assay, enzyme-linked immunoassay, high performance liquid chromatography and the like. However, no method for detecting tetracycline by adopting carbon quantum dots exists at present.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing N and S-doped water-soluble carbon quantum dots by using alliin-rich purple garlic as a novel biomass carbon source and adopting a one-step hydrothermal method.
To achieve the above object, a first technical solution provided by the present invention is as follows:
an N, S doped water-soluble carbon quantum dot, which is prepared by the following steps: mixing the garlic ground substance and water according to the volume ratio of 12-16:2, carrying out hydrothermal reaction for 20-30h at the temperature of 160-200 ℃ under a closed condition, carrying out centrifugal separation after the reaction is finished, and freeze-drying the supernatant to obtain the N, S doped water-soluble carbon quantum dots.
Further, the above N, S doped water-soluble carbon quantum dot is prepared by the following steps:
A) selecting purple-skin garlic rich in alliin, and peeling off the outer skin;
B) grinding peeled Bulbus Allii in a blender;
C) grinding to obtain a thick garlic grind.
Further, the volume ratio of the garlic ground substance to water is 14 mL: 2 mL.
Further, the temperature of the hydrothermal reaction is 180 ℃.
Further, the hydrothermal reaction time is 24 hours for the N, S doped water-soluble carbon quantum dots.
Further, the rotational speed of the centrifugal separation is 3000 r/min.
Further, the N, S doped water-soluble carbon quantum dot is prepared by centrifuging for 30 minutes.
Further, the N, S doped water-soluble carbon quantum dot is freeze-dried at the temperature of-54 ℃ for 24 hours.
The second technical scheme provided by the invention is as follows:
the N, S-doped water-soluble carbon quantum dot is applied as a tetracycline detection agent.
The invention has the beneficial effects that:
according to the method, the low-cost garlic is used as a biomass carbon source, the N and S-doped water-soluble carbon quantum dots are prepared by a simple one-step hydrothermal method, and the tetracycline can be detected by using fluorescence based on the N and S-doped water-soluble carbon quantum dots for the fluorescence quenching of the tetracycline.
Drawings
FIG. 1 is a graph showing UV-visible (1) and fluorescence (2) spectra of N, S-doped water-soluble carbon quantum dots prepared in example 1;
FIG. 2 is a graph showing the effect of tetracycline concentration on the fluorescence intensity of N, S-doped water-soluble carbon quantum dots prepared in example 1;
FIG. 3 shows the fluorescence intensity F of the N, S-doped water-soluble carbon quantum dots prepared in example 1 according to the pH value (a), the carbon quantum dot concentration (b) and the reaction time (c)0The influence of/F;
FIG. 4 shows the fluorescence spectra of (a) and (b) fluorescence intensity changes F of tetracycline, lincomycin hydrochloride, cephalexin, penicillin/streptomycin, ampicillin, trihydrate at the same concentrations0a/F-1; (c) fluorescence of each ion pair systemVariation of light intensity F0a/F-1; (d) changes in fluorescence intensity of amino acids and saccharides0/F-1；
FIG. 5 is a standard working curve for tetracycline concentration.
Detailed Description
In order to further understand the present invention, the following description will be made with reference to the examples to illustrate the N, S doped water soluble carbon quantum dots and the preparation method thereof and the method for detecting tetracycline provided by the present invention.
Example 1
The invention provides an N, S doped water-soluble carbon quantum dot which is prepared by the following steps:
1) selecting purple garlic rich in alliin, peeling, placing the peeled garlic in a stirrer for grinding, and grinding to obtain juice to obtain viscous garlic ground matter.
2) Mixing the garlic ground substance with water according to a volume ratio of 14 mL: 2mL of the mixture is mixed, the mixture is placed in a polytetrafluoroethylene reaction kettle, the reaction kettle is placed in a box-type resistance furnace after being sealed for hydrothermal reaction, the hydrothermal reaction is carried out for 20 hours at 200 ℃ under the sealed condition, 3000r/min is carried out after the reaction is finished, and the centrifugal separation is carried out for 30 minutes. And (3) taking the supernatant, and carrying out freeze drying at-54 ℃ for 24 hours to obtain the N and S doped water-soluble carbon quantum dots.
Example 2
The invention provides an N, S doped water-soluble carbon quantum dot which is prepared by the following steps:
1) selecting purple garlic rich in alliin, peeling, placing the peeled garlic in a stirrer for grinding, and grinding to obtain juice to obtain viscous garlic ground matter.
2) Mixing the garlic ground substance with water according to a volume ratio of 14 mL: 2mL of the mixture is mixed, the mixture is placed in a polytetrafluoroethylene reaction kettle, the reaction kettle is placed in a box-type resistance furnace after being sealed for hydrothermal reaction, the hydrothermal reaction is carried out for 24 hours at 180 ℃ under the sealed condition, 3000r/min is carried out after the reaction is finished, and the centrifugal separation is carried out for 30 minutes. And (3) taking the supernatant, and carrying out freeze drying at-54 ℃ for 24 hours to obtain the N and S doped water-soluble carbon quantum dots.
Example 3
The invention provides an N, S doped water-soluble carbon quantum dot which is prepared by the following steps:
1) selecting purple garlic rich in alliin, peeling, placing the peeled garlic in a stirrer for grinding, and grinding to obtain juice to obtain viscous garlic ground matter.
2) Mixing the garlic ground product with water according to a volume ratio of 14 mL: 2mL of the mixture is mixed, the mixture is placed in a polytetrafluoroethylene reaction kettle, the reaction kettle is placed in a box-type resistance furnace after being sealed for hydrothermal reaction, the hydrothermal reaction is carried out for 30 hours at 160 ℃ under the sealed condition, 3000r/min is carried out after the reaction is finished, and the centrifugal separation is carried out for 30 minutes. And (3) taking the supernatant, and carrying out freeze drying at-54 ℃ for 24 hours to obtain the N and S doped water-soluble carbon quantum dots.
Ultraviolet-visible light and fluorescence spectrum detection are performed on the N, S-doped water-soluble carbon quantum dots prepared in examples 1 to 3, and the results are shown in fig. 1, and fig. 1 is an ultraviolet-visible light (1) and fluorescence (2) spectrum diagram of the N, S-doped water-soluble carbon quantum dots prepared in example 1. As can be seen from fig. 1(1), the carbon quantum dot has an absorption peak at 280nm, which indicates that the pi-pi transition of the conjugated carbon-carbon double bond may contain functional groups such as C ═ C and C ═ O. The carbon quantum dot solution dissolved in water was observed to have a slight yellow color in daylight, while emitting bright blue fluorescence under uv light at 365 nm. To further investigate the optical properties of the obtained carbon quantum dots, fig. 1(2) shows fluorescence spectra obtained after excitation of the carbon quantum dots at 350nm using an LS45 fluorescence spectrometer. As can be seen, the carbon quantum dot has good fluorescence emission spectrum peak shape at 430nm and high fluorescence intensity, the whole emission peak covers 420-450 nm, and belongs to the blue light range, which is consistent with the blue light emission observed under an ultraviolet lamp with the wavelength of 365 nm. Therefore, 430nm is selected as the measurement wavelength in the experiment.
Example 4
The invention also provides a qualitative method for detecting tetracycline, which comprises the following steps:
1) preparing standard tetracycline sample solution to be detected
Taking 0.01mol/L dilute hydrochloric acid as a solvent, precisely weighing 10mg of tetracycline standard substance, dissolving in a small beaker with 0.01mol/L dilute hydrochloric acid, transferring to a 10mL clean brown volumetric flask, fixing the volume to a scale mark with purified water, shaking up, keeping the volume at 1mg/mL, and keeping the sample at 4 ℃ in a dark place.
2) Tetracycline with a concentration range of 0-1 mg/mL and a carbon quantum dot of 0.0129mg/mL were prepared in PBS buffer (0.01mol/L, pH 7.4) and mixed uniformly. After standing at room temperature for 5 minutes, at an excitation wavelength λexThe fluorescence spectrum was scanned at 350nm, and the change in fluorescence intensity at 430nm was measured.
The detection principle is as follows: the addition of tetracycline to the N, S-doped water-soluble carbon quantum dots significantly reduced the fluorescence intensity at 430nm, as shown in FIG. 2. Further experimental investigation shows that, in a certain concentration range, tetracycline can obviously quench the fluorescence of the carbon quantum dots, and the fluorescence intensity of the carbon quantum dots is reduced along with the increase of the concentration of the tetracycline. Meanwhile, the tetracycline-added carbon quantum dot solution has little color change under visible light and no fluorescence emission under ultraviolet light. A reasonable explanation for the decrease in fluorescence intensity of the carbon quantum dots after addition of the tetracycline solution is: the tetracycline molecule contains phenolic hydroxyl and enol groups, and can generate chemical reaction when meeting acid, and experiments prove that the carbon quantum dot solution is acidic, so that the groups on the surface of the carbon quantum dot interact with the tetracycline, and the energy of the carbon quantum dot is promoted to be captured by newly formed hydrogen bonds. Therefore, the carbon quantum dots can be used as a fluorescent probe to detect the tetracycline based on the fluorescence quenching effect of the carbon quantum dots of the garlic on the tetracycline.
In short, the N, S-doped water-soluble carbon quantum dot provided by the application has good fluorescence emission spectrum peak shape at 430nm and high fluorescence intensity under the excitation of the excitation wavelength of 350 nm; when tetracycline is added, the tetracycline can obviously quench the fluorescence of the carbon quantum dots, and the fluorescence intensity of the carbon quantum dots at 430nm is obviously reduced, as shown in FIG. 2, so that the tetracycline is detected.
Example 5
The invention also provides a method for detecting the tetracycline quantification, which comprises the following steps:
1) preparing tetracycline standard samples into tetracycline aqueous solutions (0-1 mg/mL) with different concentrations according to the preparation method of the tetracycline standard solution in the embodiment 4;
2) mixing the N-S doped water-soluble carbon quantum dots with a buffer solution (0.01mol/L, pH 7.4) to obtain a mixed solution, wherein the concentration of the N-S doped water-soluble carbon quantum dots is 0.0129mg/mL, the concentration of tetracycline is 0-1 mg/mL, and standing at room temperature for 5 minutes;
3) at an excitation wavelength λexScanning the fluorescence spectrum under the condition of 350nm, measuring the fluorescence intensity of the sample solution under the condition of 430nm to obtain different fluorescence intensities, and drawing a fitting curve of the carbon quantum dot solution fluorescence intensity along with the change of tetracycline concentration according to the fluorescence spectrogram of the standard sample solution. As shown in FIG. 5, the results showed that the tetracycline concentration was 7.63-2.5X 10 in the 0.01mol/LPBS buffer system at pH7.4 at 5 minutes5The linear relation in the ng/mL range is good, and the linear regression equation is as follows: f01576.9c-1.8943, and 0.9971.
Example 6
1. Influencing factors of the fluorescence property of the carbon quantum dots:
1) influence of the pH value of the solution on the fluorescence properties of the N and S doped water-soluble carbon quantum dots:
preparing 0.01mol/L PBS buffer solution with pH being 7.4, adjusting the pH value of the PBS buffer solution by using 0.1mol/LHCl solution and 0.2mol/LNaOH solution to respectively obtain PBS buffer solutions with pH values of 2.5, 4.8, 6.6, 8.3, 10.5 and 12.0; adding a certain amount of carbon quantum dots to make the concentration of the carbon quantum dots be 0.0129mg/mL, uniformly mixing, standing at room temperature for 5 minutes, and then exciting at the wavelength of lambdaexThe fluorescence spectrum was scanned at 350nm, and the change in fluorescence intensity at 430nm was measured (F)0/F, wherein F0Fluorescence intensity at pH7.4, and F is the fluorescence intensity of the system).
As can be seen from fig. 3(a), the fluorescence intensity of the carbon quantum dot gradually decreases as the pH increases. When the pH value is more than 10, the fluorescence intensity of the carbon quantum dots is suddenly reduced, and before the pH value is 8.0, the fluorescence intensity is basically kept unchanged, which indicates that the carbon quantum dots have good fluorescence stability under acidic, neutral or weakly alkaline conditions.
2) Influence of the concentration of the N, S-doped water-soluble carbon quantum dots on the fluorescence properties of the N, S-doped water-soluble carbon quantum dots:
a carbon quantum dot was added to PBS buffer (0.01mol/L, pH 7.4) in a predetermined amount so that the concentrations thereof were 0.1, 0.2, 0.4, 0.8, 1.6, 3.2, 6.4, and 12.9 μ g/mL, respectively, mixed uniformly, left at room temperature for 5 minutes, and then, the mixture was left at an excitation wavelength λexThe fluorescence spectrum was scanned at 350nm, and the change in fluorescence intensity at 430nm was measured (F)0/F, wherein F0Fluorescence intensity of 12.9. mu.g/mL, F is the fluorescence intensity of the system).
As shown in fig. 3(b), the fluorescence intensity increases as the concentration of the carbon quantum dots increases. According to the conclusion, when the concentration of the carbon quantum dot solution is lower, the carbon quantum dots have better dispersibility in the aqueous solution, so the fluorescence intensity is weaker; however, the concentration of the carbon quantum dot solution should not be too high, and when the concentration of the carbon quantum dot particles is in a supersaturated state, the carbon quantum dot particles are relatively easy to aggregate to form larger particles, so that the particle size is not uniform, and the fluorescence intensity of the carbon quantum dots is influenced.
3) Influence of reaction time on fluorescence properties of N, S-doped water-soluble carbon quantum dots:
tetracycline was prepared at a concentration of 0.025mg/mL and a carbon quantum dot of 0.0129mg/mL in PBS buffer (0.01mol/L, pH 7.4), and mixed uniformly. When the carbon quantum dot solution and the tetracycline solution are subjected to different reaction times (5min, 10min, 15min, 20min, 30min, 60min and 90min), the excitation wavelength is lambdaexThe fluorescence spectrum was scanned at 350nm, and the change in fluorescence intensity of the system at 430nm (F) was measured0/F, wherein F0Fluorescence intensity at 0min, F is the fluorescence intensity of the system).
As shown in FIG. 3(c), the fluorescence intensity of the system decreased after the tetracycline solution was added, and did not change much with the increase of the mixing time of the tetracycline and the carbon quantum dots, and was substantially stable after 5 min. The results show that the interaction speed of the tetracycline and the carbon quantum dots is high. Therefore, a new method for rapidly detecting tetracycline can be established based on the strong quenching effect of tetracycline on carbon quantum dot fluorescence.
2. Selective detection of tetracycline:
in PBS buffer (0.01mol/L, pH 7.4), carbon quantum dots solution with concentration of 0.0129mg/mL and tetracycline, lincomycin hydrochloride, cephalexin, penicillin/streptomycin and ampicillin trihydrate standard solution with concentration of 0.025mg/mL are prepared and mixed evenly. After standing at room temperature for 5 minutes, at an excitation wavelength λexThe fluorescence spectrum was scanned at 350nm, and the change in fluorescence intensity at 430nm was measured (F)0a/F-1, wherein F0Fluorescence intensity of reagent blank, F fluorescence intensity of system).
As shown in FIGS. 4(a) and 4(b), a significant decrease in the fluorescence intensity of the carbon quantum dots was observed after addition of the tetracycline standard solution. And after other antibiotics are added into the carbon quantum dot solution, the fluorescence intensity of the carbon quantum dot is not obviously reduced, so that the sharp contrast is formed, and the carbon quantum dot has good selectivity for detecting tetracycline.
Compared with lincomycin hydrochloride, cefalexin, penicillin/streptomycin, ampicillin and trihydrate, the tetracycline detection method provided by the invention has obvious selectivity on tetracycline.
To investigate whether the detection of tetracycline by the foreign coexisting substances had an effect, common metal ions (Mg) were added in the presence of tetracycline, respectively2+，Ca2+，Mn2+，Cu2+，Zn2+，K+，Na+，Fe2+，Fe3+，Ba2+，Al3+) Carbohydrates (glucose, sucrose, maltose) and amino acids (valine, tryptophan, phenylalanine, histidine, serine, arginine, glutamic acid, alanine, aspartic acid) as follows:
1) effect on tetracycline detection in the presence of amino acids, metal ions, sugars:
preparing an amino acid solution: accurately weighing 0.0330g of phenylalanine, 0.0178g of alanine, 0.0408g of tryptophan, 0.0210g of serine, 0.2343g of valine, 0.0348g of arginine hydrochloride and 0.0310g of histidine hydrochloride, respectively dissolving with deionized water, and fixing the volume to 100mL, wherein the concentration is 0.2 mM/L; precisely weighing 0.0294g of glutamic acid and 0.0264g of aspartic acid, dissolving with a proper amount of deionized water, neutralizing with a proper amount of potassium hydroxide solution to be neutral, transferring into a 100mL volumetric flask, and fixing the volume to a scale mark with deionized water, wherein the concentration is 0.2 mM/L;
preparing a metal ion solution: 0.117g of sodium chloride, 0.149g of potassium chloride, 0.273g of zinc chloride, 0.222g of calcium chloride, 0.338g of manganese sulfate, 0.499g of copper sulfate pentahydrate, 0.407g of magnesium chloride hexahydrate, 0.75g of aluminum nitrate nonahydrate, 0.541g of ferric trichloride hexahydrate, 0.489g of barium chloride dihydrate and 0.556g of ferrous sulfate heptahydrate are accurately weighed respectively, and are dissolved by purified water and are fixed to a constant volume of 50mL to be prepared into ionic solutions with the concentration of 40mM/L respectively, wherein the ferrous sulfate heptahydrate is easy to oxidize and discolor in the air, and a small amount of iron powder or a proper amount of dilute sulfuric acid can be added to delay oxidation in the process of preparing the solutions. Taking 1mL of mother solution, putting the mother solution in a 100mL volumetric flask, and fixing the volume to a scale mark by using purified water, wherein the concentration is 0.4 mM/L;
preparing a sugar solution: accurately weighing 0.360g of glucose, 0.072g of maltose and 0.068g of sucrose respectively, pouring into a beaker, adding a proper amount of water for dissolving, pouring into a 50mL volumetric flask, diluting with purified water to a scale mark, and fully shaking up to prepare a sugar solution with the concentration of 40 mM/L. 1mL of the mother solution was taken and put in a 100mL volumetric flask, and the volume was determined to the scale mark with purified water, and the concentration was 0.4 mM/L.
2mL of a carbon quantum dot solution (0.0129 mg/mL), 0.5mL of a tetracycline solution (0.025 mg/mL), 0.5mL of a PBS buffer (0.01mol/L, pH 7.4), and 0.5mL of an amino acid or metal ion or sugar solution (0.4 mM/L) were added to a 4mL cuvette in this order, and the mixture was mixed uniformly. After standing at room temperature for 5 minutes, at an excitation wavelength λexThe fluorescence spectrum was scanned at 350nm, and the change in fluorescence intensity at 430nm was measured (F)0a/F-1, wherein F0Fluorescence intensity of reagent blank, F fluorescence intensity of system).
As a result, Fe was found to be present in FIGS. 4(c) and 4(d)3+、Fe2+Has obvious quenching effect on the fluorescence intensity of the carbon quantum dots, probably due to Fe3+、Fe2+The reason for stronger acting force between the carboxyl, hydroxyl and amino on the surface of the carbon quantum dot。Mg2+、Ca2+、Mn2+、Cu2+、Zn2+、K+、Na+、Ba2+、Al3+Valine, tryptophan, phenylalanine, histidine, serine, arginine, glutamic acid, alanine, aspartic acid, glucose, maltose and sucrose have no obvious change on the fluorescence signal of the carbon quantum dot. Therefore, based on the quenching effect of tetracycline on carbon quantum dot fluorescence, when the method is used for detecting an actual tetracycline sample, sample pretreatment is required, so that Fe is eliminated3+、Fe2+Interference effect of (3).
And Mg2+、Ca2+、Mn2+、Cu2+、Zn2+、K+、Na+、Ba2+、Al3+Glucose, maltose, sucrose, valine, tryptophan, phenylalanine, histidine, serine, arginine, glutamic acid, alanine and aspartic acid have no obvious change to the carbon quantum dot fluorescence signal, and the experimental result shows that the method for detecting tetracycline by using the N, S-doped water-soluble carbon quantum dot has good anti-interference performance.
The application example is used for detecting the tetracycline in the tetracycline tablet by an actual sample:
1 tetracycline tablet (specification: 0.25g, lot number: 140911) provided by Guangdong south China pharmaceutical industry group Co., Ltd.) was taken out, put into a mortar, ground into powder, dissolved with 0.01mol/L of dilute hydrochloric acid and filtered, and then dissolved in a 100mL volumetric flask with purified water. Accurately transferring 100uL of the prepared tetracycline solution, and fixing the volume to 10mL by using purified water to obtain a tetracycline tablet sample solution to be detected, wherein the concentration is 0.025 mg/mL;
then, the recovery rate was measured, and 0.375mL of tetracycline tablet sample solution, 0.375mL of a control tetracycline solution having a known and accurate content, 0.75mL of PBS buffer (0.01mol/L, pH 7.4), and 1.5mL of carbon quantum dot solution were sequentially added to a 3mL cuvette, and mixed uniformly. Standing at room temperature for 5min, and exciting at excitation wavelength lambdaexScanning fluorescence spectrum at 350nm, measuring fluorescence intensity at 430nm, measuring in parallel for 3 times, and calculating the absorbance of the sampleThe yields and Relative Standard Deviations (RSD) are shown in Table 1.
TABLE 1
Table 1 shows the results of measuring the content of tetracycline in the actual samples. Therefore, the Relative Standard Deviation (RSD) of the tested sample is between 0.73% and 0.76%, the sample recovery rate is between 81.66% and 93.81%, and the result is satisfactory, which indicates that the method meets the analysis and determination requirements and can be used for quantitative detection of tetracycline.
The tetracycline detection method provided by the invention can be used for qualitative and quantitative detection of tetracycline in various substances containing tetracycline.
Claims (8)
1. The application of the N, S doped water-soluble carbon quantum dot as a tetracycline detection agent is characterized in that the N, S doped water-soluble carbon quantum dot is prepared by the following method: mixing the garlic ground substance and water according to the volume ratio of 12-16:2, carrying out hydrothermal reaction for 20-30h at the temperature of 160-200 ℃ under a closed condition, carrying out centrifugal separation after the reaction is finished, and freeze-drying the supernatant to obtain the N, S doped water-soluble carbon quantum dots.
2. The application of the N, S-doped water-soluble carbon quantum dot as the tetracycline detection agent according to claim 1, wherein the garlic ground substance is prepared by the following steps:
A) selecting purple-skin garlic rich in alliin, and peeling off the outer skin;
B) grinding peeled Bulbus Allii in a blender;
C) grinding to obtain a thick garlic grind.
3. The application of the N, S-doped water-soluble carbon quantum dot as the tetracycline detection agent according to claim 1, wherein the volume ratio of the garlic ground substance to water is 14 mL: 2 mL.
4. The application of the N, S-doped water-soluble carbon quantum dot as the tetracycline detection agent in claim 1, wherein the temperature of the hydrothermal reaction is 180 ℃.
5. The application of the N, S-doped water-soluble carbon quantum dot as the tetracycline detection agent in claim 1, wherein the hydrothermal reaction time is 24 hours.
6. The application of the N, S-doped water-soluble carbon quantum dot as the tetracycline detection agent in claim 1, wherein the rotation speed of the centrifugal separation is 3000 r/min.
7. The application of the N, S-doped water-soluble carbon quantum dot as the tetracycline detection agent in claim 1, wherein the time for centrifugal separation is 30 minutes.
8. The application of the N, S-doped water-soluble carbon quantum dot as the tetracycline detection agent in claim 1, wherein the freeze-drying temperature is-54 ℃, and the freeze-drying time is 24 hours.
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