CN113884475B - Tetracycline detection method based on europium-doped carbon quantum dot ratio fluorescent probe - Google Patents
Tetracycline detection method based on europium-doped carbon quantum dot ratio fluorescent probe Download PDFInfo
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a tetracycline detection method based on a europium-doped carbon quantum dot ratio fluorescent probe, and belongs to the technical field of tetracycline detection. According to the tetracycline detection method based on the europium-doped carbon quantum dot ratio fluorescent probe, according to the characteristic that the tetracycline can enable the europium-doped carbon quantum dot ratio fluorescent probe to generate remarkable color change from blue to brown yellow to light purple to light rose red to light pink to final red, the fluorescence intensity change I of a sample to be detected and Eu-CDs mixed solution is detected 620 /I 468 Comparing the standard curve to obtain the tetracycline content in the sample to be detected; in addition, the paper-based sensor containing the europium-doped carbon quantum dot ratio fluorescent probe is prepared, the smart phone is used as a signal reader, the smart phone is convenient to carry, the on-site detection of the tetracycline in a resource limited environment can be realized, and the detection method is simple, sensitive and efficient.
Description
Technical Field
The invention belongs to the technical field of tetracycline detection, and particularly relates to a tetracycline detection method based on a europium-doped carbon quantum dot ratio fluorescent probe.
Background
Tetracyclines (TCs) are an important common antibiotic that has found wide application in animal husbandry, aquaculture and personalized therapy due to their low cost, high antimicrobial activity, good oral absorption, low toxicity. Unfortunately, there have been serious adverse effects on food safety, environmental protection, and human health due to excessive use of TC products. Currently, there are a number of analytical strategies for detecting tetracyclines, such as liquid chromatography-mass spectrometry (LC-MS), high Performance Liquid Chromatography (HPLC), capillary Electrophoresis (CE), chemiluminescence and electrochemical analysis, which allow accurate detection of tetracyclines. However, the defects of strict instrument requirements, time consumption, complicated step operation, requirement on professional skills and the like exist. In recent years, fluorescence sensors or fluorescence analysis techniques have been successfully applied to the measurement of TC with the advantages of simple operation, rapid response speed, low detection limit, small sample amount, good selectivity, low analysis cost, and the like. Notably, europium-based fluorescent sensing platforms exhibit highly enhanced fluorescence when bound to TC, which has attracted considerable attention in recent years. This can be attributed to the fact that TC can react with europium ions (Eu 3+ ) Bind to form europium-tetracycline complex (Eu 3+ -TC) and transfer energy absorbed by tetracycline to Eu 3+ Making Eu 3+ Is greatly enhanced, which is referred to as "antenna effect". Furthermore, eu 3+ Has unique spectral characteristics including large Stokes shift, long fluorescence lifetime, and sharp linear emission region. However, europium-bound tetracyclines have a weak fluorescence intensity due to quenching effect caused by oscillation modes of coordinated water molecules. Furthermore, these europium-based sensor platforms are limited in practical applications due to poor stability in humid environments and ultraviolet light.
Disclosure of Invention
The invention aims to provide a tetracycline detection method based on a europium-doped carbon quantum dot ratio fluorescent probe, which comprises the following steps:
(1) Preparing a europium-doped carbon quantum dot ratio fluorescent probe into an aqueous solution, namely a Eu-CDs solution;
(2) Adding different amounts of tetracycline into the Eu-CDs solution prepared in the step (1), preparing the Eu-CDs solution into standard solutions with different concentration gradients of the tetracycline, and uniformly mixing the solutions;
(3) Recording fluorescence intensities at 468nm and 620nm of standard solutions with different tetracycline concentration gradients under 380nm excitation by adopting a fluorescence spectrometry;
(4) The experimental data obtained in the step (3) are arranged and plotted as I 620 /I 468 The intensity ratio of (2) is taken as an ordinate, the tetracycline concentration is taken as an abscissa, and the tetracycline concentration and I are obtained 620 /I 468 A linear equation of the intensity ratio;
(5) Mixing the sample solution to be detected with the Eu-CDs solution prepared in the step (1); obtaining fluorescence intensity at 468nm and 620nm of the solution to be detected by adopting a fluorescence spectrum method under excitation of 380nm, and calculating I 620 /I 468 Substituting the obtained linear equation in the step (4), and calculating to obtain the content of the tetracycline in the sample solution to be detected.
In the tetracycline detection method based on the europium-doped carbon quantum dot ratio fluorescent probe, the europium-doped carbon quantum dot ratio fluorescent probe is prepared by the following method:
dissolving 8.0-12 mmol of citric acid and 0.2-0.3 mmol of melamine in water, and then adding 0-1000 mu L of formaldehyde solution and 300-800 mg of Eu (NO) 3 ) 3 ·6H 2 O; after the solution is fully mixed, reacting for 5 to 10 hours at the temperature of 180 to 220 ℃; cooling to room temperature after the reaction is finished, filtering and dialyzing the obtained solution to remove small molecules with molecular weight less than 1000 Da; and drying to obtain europium-doped carbon quantum dot ratio fluorescent probe powder.
In a specific embodiment, the formaldehyde solution has a concentration of 8mmol/L.
In a specific embodiment, the citric acid is used in an amount of 10mmol; the amount of melamine is 0.25mmol; eu (NO) 3 ) 3 ·6H 2 The dosage of O is 500mg; the quantum yield was highest when the formaldehyde solution was used in an amount of 560. Mu.L.
In a specific embodiment, the Eu-CDs solution in step (1) has a concentration of 60. Mu.g.mL -1 。
In a specific embodiment, the mixing ratio of the sample solution to be measured in the step (5) and the Eu-CDs solution is 1:1.
In a specific embodiment, the concentration of the standard solution of tetracycline in the different concentration gradients is in the range of 0-100. Mu.M.
In a specific embodiment, the dialysis is performed by first filtering with a 0.22 μm filter membrane, dialyzing the filtrate in ultra pure water for 24 hours using a dialysis bag with a cutoff molecular weight of 1000Da, and refreshing the water every 6 hours to remove small molecules.
The second object of the invention is to provide a paper-based sensor for detecting tetracycline, which is to immerse filter paper in an aqueous solution of a europium-doped carbon quantum dot ratio fluorescent probe; incubating at room temperature for a period of time, and drying to obtain the paper-based sensor for detecting tetracycline;
the europium-doped carbon quantum dot ratio fluorescent probe is prepared by the following method:
dissolving 8.0-12 mmol of citric acid and 0.2-0.3 mmol of melamine in water, and then adding 0-1000 mu L of formaldehyde solution and 300-800 mg of Eu (NO) 3 ) 3 ·6H 2 O; after the solution is fully mixed, reacting for 5 to 10 hours at the temperature of 180 to 220 ℃; cooling to room temperature after the reaction is finished, filtering and dialyzing the obtained solution to remove small molecules with molecular weight less than 1000 Da; and drying to obtain europium-doped carbon quantum dot ratio fluorescent probe powder.
In a specific embodiment, the concentration of the aqueous solution of the europium-doped carbon quantum dot ratio fluorescent probe is 60. Mu.g.mL -1 。
The filter paper can be cut into different shapes according to the requirements, and the skilled person will understand that the shape of the filter paper does not influence the detection result; in a specific embodiment, the filter paper is cut into circles with a diameter of 6 mm.
In a specific embodiment, the room temperature incubation is room temperature incubation for 10min.
The invention further aims to provide an application of the paper-based sensor for detecting the tetracycline in a tetracycline detection method taking a smart phone as a signal reader.
The fourth object of the present invention is to provide a tetracycline detection method using a smart phone as a signal reader, comprising the following steps:
(1) Adding tetracycline standard solutions with different concentrations to the surface of the paper-based sensor;
(2) Downloading and installing a color scanning application program on the smart phone;
(3) Recording the fluorescent color of the paper-based sensor in the step (1) under a 365nm ultraviolet lamp by using a color scanning application program on the smart phone, and digitizing and outputting the fluorescent color of the paper-based sensor to obtain an RG B value; using R/B as an ordinate and the concentration of the tetracycline as an abscissa, and obtaining a linear equation of the concentration of the tetracycline and the R/B;
(4) Adding a sample solution to be measured to the surface of the paper-based sensor;
(5) Recording the fluorescent color of the paper-based sensor in the step (4) under a 365nm ultraviolet lamp by using a color scanning application program on the smart phone, and digitizing and outputting the fluorescent color of the paper-based sensor to obtain an RG B value; calculating R/B; substituting the value of R/B into the linear equation obtained in the step (3), and calculating to obtain the content of the tetracycline in the sample solution to be detected.
The above description of the amounts of raw materials is merely an operational amount of a laboratory, not an absolute limitation of the amounts thereof, and it will be understood by those skilled in the art that in actual production, the amounts may be adjusted in accordance with the above-mentioned proportions according to the production scale.
The method for detecting the tetracycline is applicable to matrix samples such as aqueous solution and the like, such as water body and milk; the solid sample may be prepared in the form of an aqueous solution or may be tested after filtration to remove water insoluble components.
In the steps (1) and (4), the addition amounts of the tetracycline standard solutions or the sample solutions to be detected with different concentrations on the paper-based sensor can be adjusted according to the size of the test paper sheet used for preparing the paper-based sensor; in a specific embodiment of the invention, the test paper sheet is in the shape of a circular sheet with the diameter of 6mm, and the addition amount of the tetracycline standard solution or the sample solution to be tested with different concentrations on the test paper sheet is 200 mu L/sheet.
The europium-doped carbon quantum dot provided by the invention is prepared and the tetracycline detection principle is as follows: europium ions are doped into the lattice structure of the carbon quantum dots as specific recognition units of TC. When no tetracycline was added, the europium-doped carbon quantum dots fluoresced blue (λem=420 nm). Based on Internal Filtration Effect (IFE) and Eu after binding to tetracycline 3+ -the "antenna effect" of TC, the blue fluorescence of the carbon quantum dots is gradually quenched, the characteristic red fluorescence of the doped europium element is gradually increased (λem=620 nm), yielding a ratiometric fluorescence signal change based on tetracycline content. Correspondingly, the color of the detection system under the ultraviolet lamp gradually changes from blue to brown yellow to light purple to light rose red to light pink to final red.
The technical scheme of the invention has the advantages that:
the europium-doped carbon quantum dot ratio fluorescent probe is prepared by a one-step hydrothermal method. Europium ions are doped into the carbon quantum dots, so that blue fluorescence of the carbon quantum dots can be maintained, and red fluorescence of the europium ions can be enhanced by specific combination with tetracycline molecules, and a ratio fluorescence signal and obvious gradual change of color are generated. The novel fluorescent probe has excellent physical and chemical stability, does not need complex carbon quantum dot modification, can realize the ratio fluorescent detection of target molecules through a single carbon quantum dot, and can observe the remarkable change from blue to brown yellow to light purple to light rose red to light pink to final red of the carbon quantum dot gradually by naked eyes under an ultraviolet lamp.
In addition, a portable paper-based sensor without instruments and a smart phone-assisted POCT platform for on-site visual detection of tetracycline have been developed. The developed paper-based sensor has the characteristics of easy carrying, low cost, high selectivity and high sensitivity, and can directly and easily read out detection signals by naked eyes. The smart phone is used as a simple answer analyzer and has the characteristics of portability and easy operation. When the concentration of TC exceeds a certain level, a visual direct color change alerts the user that further cell phone assisted image processing can provide a quantitative analysis of tetracycline concentration. Provides a powerful method for qualitative identification and semi-quantitative analysis of tetracyclines in sites and areas with poor resources. And shows great potential application in food safety monitoring. Not only provides a new strategy for ratiometric fluorescence and visual sensing of tetracyclines, but also provides new insights for developing efficient ratiometric fluorescence and visual sensing platforms that are promising for many other in-situ assays in the future.
Drawings
FIG. 1 TEM analysis and HRTEM of europium-doped carbon quantum dot ratio fluorescent probe;
FIG. 2 Eu-X-ray photoelectron spectroscopy (XPS) of CDs;
FIG. 3 effect of europium doping concentration on fluorescence spectrum of Eu-CDs-TC complex;
FIG. 4 is a fluorescence spectrum of the effect of different concentrations TC on Eu-CDs fluorescence intensity;
FIG. 5 is a linear equation for detecting tetracycline with europium-doped carbon quantum dot ratio fluorescent probes;
FIG. 6 specificity of europium-doped carbon quantum dot ratio fluorescent probes for tetracycline;
fig. 7 is a linear equation for detecting tetracycline based on europium-doped carbon quantum ratio fluorescent probes in combination with smart phones and paper-based sensors.
Detailed Description
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated.
The invention will be described in further detail below in connection with specific embodiments and with reference to the data. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1
The preparation method of the europium-doped carbon quantum dot ratio fluorescent probe comprises the following steps:
1920mg (10.0 mmol) of citric acid and 31.5mg (0.25 mmol) of melamine were weighed out and dissolved in 10mL of ultrapure water, and then 560. Mu.L of formaldehyde solution (formaldehyde concentration: 8.0 mmol/L) and 500mg of Eu (NO) were added 3 ) 3 ·6H 2 O (99.99%). The solution was thoroughly mixed, transferred to a 25mL polytetrafluoroethylene-lined stainless steel autoclave, reacted at 220 ℃ for 10 hours, cooled to room temperature, and the resulting deep yellow solution was filtered through a 0.22 μm filter membrane and further dialyzed in ultra pure water with a dialysis bag (cut molecular weight 1000 Da) for 24 hours, with water being renewed every 6 hours to remove small molecules. Subsequently, by evaporating the solution in the dialysis bag and drying at 80 ℃, a powder of the europium-doped carbon quantum dot ratio fluorescent probe was obtained with a quantum yield of 10.81%.
FIG. 1 is a Transmission Electron Microscope (TEM) image and a High Resolution Transmission Electron Microscope (HRTEM) image of a europium-doped carbon quantum dot ratio fluorescent probe (Eu-CDs) prepared by the above method. As can be seen from a in FIG. 1, eu-CDs are uniformly distributed near-spherical nanoparticles, and the Eu-CDs particle size distribution histogram shows that the particle size distribution is 1.0-3.0nm and the average particle size is 2.0nm. The HRTEM image (b in fig. 1) shows that Eu-CDs have sharp lattice fringes, with a lattice spacing of about 0.20nm, which coincides with the (100) plane of graphitic carbon.
In order to confirm the elemental composition and chemical bond of Eu-CDs, X-ray photoelectron spectroscopy (XPS) measurement was performed. FIG. 2 is an XPS plot of Eu-CDs, where a is the XPS full scan spectrum of Eu-CDs, b is the XPS spectrum of C1s, C is the XPS spectrum of N1s, d is the XPS spectrum of O1s, and e is the XPS spectrum of Eu3 d;
as can be seen from FIG. 2, XPS full scan spectra showed four distinct peaks at 281.08,398.08,537.08 and 1131.08eV, due to C1s, N1s, O1s and Eu3d, with element contents of 60.11%,2.99%,33.03% and 3.87%, respectively. High levels of Eu confirm the successful doping of Eu in CDs (a in FIG. 2). In high resolution spectra (fig. 2 b-e), the C1s band can deconvolute into three peaks at 284.7,285.7 and 288.4eV, corresponding to C-C/c=c, C-N/C-O and c=o groups, respectively; in the N1s spectrum, peaks at 399.9 and 401.5eV correspond to N-C and N-H groups; the O1s wave band is 531.2, 532.0 and 532.9eV, and can be reverse-pleatedThree peaks are integrated, respectively attributed to c=o and c—oh groups. Eu3d at 1134.0 and 1164.0eV, respectively, is attributed to 3d 5/2 And 3d 3/2 Photoemission of the structure. The high resolution Eu3d spectrum consists of four peaks, eu 3+ (1165.0 and 1135.4 eV) and Eu 2+ (1155.0 and 1125.5 eV).
Example 2
The preparation method of the europium-doped carbon quantum dot ratio fluorescent probe comprises the following steps:
1536mg (8.0 mmol) of citric acid and 25.2mg (0.2 mmol) of melamine were weighed out and dissolved in 10mL of ultra pure water, and then 300mg of Eu (NO) was added 3 ) 3 ·6H 2 O (99.99%). The solution was thoroughly mixed, transferred to a 25mL polytetrafluoroethylene-lined stainless steel autoclave, reacted at 220 ℃ for 10 hours, cooled to room temperature, and the resulting deep yellow solution was filtered through a 0.22 μm filter membrane and further dialyzed in ultra pure water with a dialysis bag (cut molecular weight 1000 Da) for 24 hours, with water being renewed every 6 hours to remove small molecules. Subsequently, by evaporating the solution in the dialysis bag and drying at 80 ℃, a powder of the europium-doped carbon quantum dot ratio fluorescent probe was obtained with a quantum yield of 7.50%.
Example 3
The preparation method of the europium-doped carbon quantum dot ratio fluorescent probe comprises the following steps:
2304mg (12.0 mmol) of citric acid and 37.8mg (0.3 mmol) of melamine were weighed out and dissolved in 10mL of ultrapure water, and then 1000. Mu.L of formaldehyde solution (formaldehyde concentration: 8.0 mmol/L) and 800mg of Eu (NO) were added 3 ) 3 ·6H 2 O (99.99%). The solution was thoroughly mixed, transferred to a 25mL polytetrafluoroethylene-lined stainless steel autoclave, reacted at 220 ℃ for 10 hours, cooled to room temperature, and the resulting deep yellow solution was filtered through a 0.22 μm filter membrane and further dialyzed in ultra pure water with a dialysis bag (cut molecular weight 1000 Da) for 24 hours, with water being renewed every 6 hours to remove small molecules. Subsequently, by evaporating the solution in the dialysis bag and drying at 80 ℃, a powder of europium-doped carbon quantum dot ratio fluorescent probe was obtained with a quantum yield of 9.02%.
Example 4
Effect of europium doping concentration on fluorescence spectrum of Eu-CDs-TC Complex
Based on the method of example 1, eu (NO 3 ) 3 ·6H 2 The doping concentrations of O are 300mg, 500mg and 800mg respectively, and different Eu (NO) are prepared 3 ) 3 ·6H 2 Eu-CDs with O doping concentration; and detecting the fluorescence spectrum after TC is added, the result is shown in figure 3, and the fluorescence spectrum shows strong doping concentration dependence as can be seen from a fluorescence intensity curve and a fluorescence intensity photo, and the fluorescence intensity enhancement amplitude of Eu-CDs-TC is increased as the Eu doping concentration is increased from 300mg to 500mg; after Eu doping concentration exceeds 500mg, fluorescence intensity is reduced due to newly generated defects and reduced surface passivation, and the fluorescence intensity enhancement amplitude of Eu doping concentration 800mg is lower than that of a 500mg Eu doped sample; thus, 500mg doped Eu-CDs produced the highest fluorescence intensity enhancement after interaction with TC compared to other doping concentrations. Therefore, the Eu doping concentration of 500mg is the optimal concentration.
Example 5
A method for detecting tetracycline, comprising the steps of:
(1) The europium-doped carbon quantum dot ratio fluorescent probe prepared in example 1 was prepared to a concentration of 60. Mu.g.mL -1 The aqueous solution of (2) is Eu-CDs solution;
(2) Adding different amounts of tetracyclines into the Eu-CDs solution prepared in the step (1) to prepare standard solutions with different concentration gradients of tetracyclines, wherein the concentration of tetracyclines is 0-100 mu M; after being evenly mixed, the mixture is cultured for 5min at room temperature;
(3) Recording the emission spectra of the standard solutions with different concentration gradients of the tetracycline under the excitation of 380nm by adopting a fluorescence spectrometry; the results are shown in FIG. 4; as can be seen from FIG. 4, the Eu-CDs system showed a significant decrease in fluorescence intensity at 468nm and a gradual increase in fluorescence intensity at 620nm with increasing tetracycline concentration. F when the tetracycline concentration is higher than 80. Mu.M 468 In a quenched state, but F 620 No longer increases and begins to decline.
(4) The obtained experimental data are arranged asFigure, at I 620 /I 468 As ordinate, TC concentration as abscissa, a linear equation is obtained as shown in fig. 5, the linear relation being y=0.0630 x-0.242; linear correlation coefficient R 2 ＝0.999。
(5) Mixing the sample solution to be detected with the Eu-CDs solution prepared in the step (1) according to the proportion of 1:1, and culturing for 5min at room temperature; obtaining fluorescence intensity at 468nm and 620nm of the solution to be detected by adopting a fluorescence spectrum method under excitation of 380nm, and calculating I 620 /I 468 And (3) comparing the intensity ratio of the sample solution to be detected with the standard curve obtained in the step (4), and calculating to obtain the content of the tetracycline in the sample solution to be detected.
The method for detecting the tetracycline has good stability and high repeatability, and the detection limit is 6.9nM.
Specificity of europium-doped carbon Quantum dot ratio fluorescent probes for Tetracycline:
the same concentration (100. Mu.M) of Tetracycline (tetracyclic) and analogues thereof (Oxytetracycline, erythromycin) solutions were mixed with equal volumes of the Eu-CDs solution prepared in step (1), respectively, and after incubation at room temperature for 5 minutes, the emission spectra of the mixture were recorded under excitation at 380nm using fluorescence spectrometry. As shown in FIG. 6, only tetracycline causes fluorescence quenching at 468nm for Eu-CDs and a strong new fluorescence emission peak at 620 nm.
Example 6
A method for detecting tetracycline based on europium-doped carbon quantum dot ratio fluorescent probe combined with a smart phone and a paper-based sensor comprises the following steps:
(1) The europium-doped carbon quantum dot ratio fluorescent probe prepared in example 1 was prepared to a concentration of 60. Mu.g.mL -1 Is an aqueous solution of (a);
(2) Cutting the filter paper into a round shape having a diameter of about 6mm, and immersing Eu-CDs (60. Mu.g.mL) prepared in the step (1) -1 ) In solution; incubating at room temperature for 10min, and drying in air at room temperature; obtaining a paper-based sensor for detecting tetracycline;
(3) Adding TC aqueous solutions with different concentrations (0-150 mu M) to the surface of the circular paper-based sensor prepared in the step (2); an addition amount of 200. Mu.L/sheet paper-based sensor;
(4) The change in fluorescence color of the circular paper-based sensor was visually observed under an ultraviolet lamp. The fluorescent color of the paper-based sensor is digitized and output through a color scanning application program (APP: color) obtained by downloading in an application store, and an R GB value is obtained; the obtained experimental data (R/B) are used for finishing and plotting to obtain a linear equation (figure 7), wherein the linear relation is Y=0.049x-0.219; linear correlation coefficient R 2 ＝0.998。
(5) Adding a sample solution to be detected to the surface of the paper-based sensor prepared in the step (2); an addition amount of 200. Mu.L/sheet paper-based sensor; recording the fluorescent color of the paper-based sensor under the ultraviolet lamp by using a color scanning application program on the smart phone, and digitizing and outputting the fluorescent color of the paper-based sensor to obtain an RGB value; calculating R/B; substituting the value of R/B into the linear equation obtained in the step (4), and calculating to obtain the content of the tetracycline in the sample solution to be detected.
The method for detecting the tetracycline has good stability and high repeatability, and the detection limit is 13.2nM.
In conclusion, the europium-doped carbon quantum dot ratio fluorescent probe synthesized by the invention not only provides a new strategy for TC ratio fluorescence and visual sensing, but also provides a new insight for developing an efficient ratio fluorescence and visual sensing platform.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (9)
1. The tetracycline detection method based on the europium-doped carbon quantum dot ratio fluorescent probe is characterized by comprising the following steps of:
(1) Preparing a europium-doped carbon quantum dot ratio fluorescent probe into an aqueous solution, namely a Eu-CDs solution;
(2) Adding different amounts of tetracycline into the Eu-CDs solution prepared in the step (1), preparing the Eu-CDs solution into standard solutions with different concentration gradients of the tetracycline, and uniformly mixing the solutions;
(3) Recording fluorescence intensities at 468nm and 620nm of standard solutions with different tetracycline concentration gradients under 380nm excitation by adopting a fluorescence spectrometry;
(4) The experimental data obtained in the step (3) are arranged and plotted as I 620 /I 468 The intensity ratio of (2) is taken as an ordinate, the tetracycline concentration is taken as an abscissa, and the tetracycline concentration and I are obtained 620 /I 468 A linear equation of the intensity ratio;
(5) Mixing the sample solution to be detected with the Eu-CDs solution prepared in the step (1); obtaining fluorescence intensity at 468nm and 620nm of the solution to be detected by adopting a fluorescence spectrum method under excitation of 380nm, and calculating I 620 /I 468 Substituting the obtained solution into the linear equation obtained in the step (4), and calculating to obtain the content of the tetracycline in the sample solution to be detected;
the europium-doped carbon quantum dot ratio fluorescent probe is prepared by the following method:
dissolving 8.0-12 mmol of citric acid and 0.2-0.3 mmol of melamine in water, and then adding 0-1000 mu L of formaldehyde solution and 300-800 mg of Eu (NO) 3 ) 3 ·6H 2 O; after the solution is fully mixed, reacting for 5 to 10 hours at the temperature of 180 to 220 ℃; cooling to room temperature after the reaction is finished, filtering and dialyzing the obtained solution to remove small molecules with molecular weight less than 1000 Da; and drying to obtain europium-doped carbon quantum dot ratio fluorescent probe powder.
2. The method for detecting tetracycline based on europium-doped carbon quantum dot ratio fluorescent probe of claim 1, wherein the concentration of the formaldehyde solution is 8mmol/L.
3. The method for detecting tetracycline based on europium-doped carbon quantum dot ratio fluorescent probe of claim 2, wherein the amount of citric acid is 10mmol; the trimerizationThe amount of cyanamide was 0.25mmol; eu (NO) 3 ) 3 ·6H 2 The dosage of O is 500mg; the formaldehyde solution was used in an amount of 560. Mu.L.
4. The method for detecting tetracycline based on europium-doped carbon quantum dot ratio fluorescent probe of claim 1, wherein the concentration of the Eu-CDs solution in step (1) is 60. Mu.g.mL -1 。
5. The method for detecting tetracycline based on europium-doped carbon quantum dot ratio fluorescent probe of claim 4, wherein the mixing ratio of the sample solution to be detected and the Eu-CDs solution in step (5) is 1:1.
6. The method for detecting tetracycline according to any one of claims 1-5, wherein said standard solutions of different concentration gradients of tetracycline have a concentration range of 0-100 μm.
7. A paper-based sensor for detecting tetracycline is characterized in that filter paper is immersed in an aqueous solution of a europium-doped carbon quantum dot ratio fluorescent probe; incubating at room temperature for a period of time, and drying to obtain the paper-based sensor for detecting tetracycline;
the europium-doped carbon quantum dot ratio fluorescent probe is prepared by the following method:
dissolving 8.0-12 mmol of citric acid and 0.2-0.3 mmol of melamine in water, and then adding 0-1000 mu L of formaldehyde solution and 300-800 mg of Eu (NO) 3 ) 3 ·6H 2 O; after the solution is fully mixed, reacting for 5 to 10 hours at the temperature of 180 to 220 ℃; cooling to room temperature after the reaction is finished, filtering and dialyzing the obtained solution to remove small molecules with molecular weight less than 1000 Da; and drying to obtain europium-doped carbon quantum dot ratio fluorescent probe powder.
8. Use of the paper-based sensor for detecting tetracycline of claim 7 in a method for detecting tetracycline in a smart phone as signal reader.
9. A tetracycline detection method taking a smart phone as a signal reader is characterized by comprising the following steps:
(1) Adding different concentrations of tetracycline standard solutions to the surface of the paper-based sensor of claim 7;
(2) Downloading and installing a color scanning application program on the smart phone;
(3) Recording the fluorescent color of the paper-based sensor in the step (1) under the ultraviolet lamp by using a color scanning application program on the smart phone, and digitizing and outputting the fluorescent color of the paper-based sensor to obtain an RG B value; using R/B as an ordinate and the concentration of the tetracycline as an abscissa, and obtaining a linear equation of the concentration of the tetracycline and the R/B;
(4) Adding a sample solution to be measured to the paper-based sensor surface of claim 7;
(5) Recording the fluorescent color of the paper-based sensor in the step (4) under the ultraviolet lamp by using a color scanning application program on the smart phone, and digitizing and outputting the fluorescent color of the paper-based sensor to obtain an RG B value; calculating R/B; substituting the value of R/B into the linear equation obtained in the step (3), and calculating to obtain the content of the tetracycline in the sample solution to be detected.
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