CN112147117A - Aminoglycoside antibiotic detection method based on fluorescent metal organic framework material - Google Patents
Aminoglycoside antibiotic detection method based on fluorescent metal organic framework material Download PDFInfo
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- 239000002647 aminoglycoside antibiotic agent Substances 0.000 title claims abstract description 53
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 35
- 229940126574 aminoglycoside antibiotic Drugs 0.000 title claims abstract description 14
- 238000001514 detection method Methods 0.000 title claims abstract description 14
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- 238000000034 method Methods 0.000 claims abstract description 22
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- 230000000694 effects Effects 0.000 claims abstract description 5
- 230000003313 weakening effect Effects 0.000 claims abstract description 5
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- YVQVOQKFMFRVGR-VGOFMYFVSA-N 5-(morpholin-4-ylmethyl)-3-[(e)-(5-nitrofuran-2-yl)methylideneamino]-1,3-oxazolidin-2-one Chemical compound O1C([N+](=O)[O-])=CC=C1\C=N\N1C(=O)OC(CN2CCOCC2)C1 YVQVOQKFMFRVGR-VGOFMYFVSA-N 0.000 description 2
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Images
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to an aminoglycoside antibiotic detection method based on a fluorescent metal organic framework material, which is based on the water instability of the fluorescent metal organic framework material and the competitive coordination effect of amino groups in aminoglycoside antibiotics on metal ions, so that the structure of the metal organic framework material is promoted to be gradually disintegrated, and the content of aminoglycoside antibiotics is determined through the signal change of firstly weakening fluorescence and then strengthening the fluorescence. The invention adopts water-instable fluorescent metal organic framework Zn-TCPE and ligand H thereof4TCPE has aggregation-induced emission properties. The coordination of Zn and carboxylic acid in the Zn-TCPE in aqueous solution is weakened or disappeared, so that the benzene ring and the carbon-carbon double bond in the ligand are distorted and vibrated, and the fluorescence is weakened. When aminoglycoside antibiotics are added, the amino group in the aminoglycoside antibiotics can be used for the Zn in Zn-TCPE2+The competitive coordination of the Zn-TCPE leads to the disintegration of the Zn-TCPE structure, the release of the ligand and the aggregation, thereby enhancing the fluorescence. The method is sensitive and convenient to detect.
Description
Technical Field
The invention relates to a detection method for measuring aminoglycoside antibiotics, in particular to a detection method for aminoglycoside antibiotics based on a fluorescent metal organic framework material. The invention belongs to the field of chemical detection.
Background
The aminoglycoside antibiotic is a glycoside antibiotic medicine formed by connecting aminosugar and aminocyclitol through an oxygen bridge. Aminoglycoside antibiotics are widely used in animal husbandry due to their good water solubility, low cost and broad spectrum antibacterial properties. However, excessive and erroneous use of aminoglycoside antibiotics results in a large amount of residues in animal derived foods and the environment, which can cause serious side effects on human health, such as allergy, nephrotoxicity, ototoxicity, and the like.
Currently, common methods for detecting aminoglycoside antibiotics include: resonance Rayleigh scattering spectrometry, spectrophotometry, capillary electrophoresis, ion exchange, high performance liquid chromatography, etc. These methods have various characteristics, but also have certain limitations, such as high detection limit, poor repeatability, expensive equipment, complex sample preparation, long test period, and the like. Therefore, a new fluorescence analysis method for detecting aminoglycoside antibiotic residues, which is simple and convenient to operate, high in sensitivity and fast in response, is needed to be established.
The fluorescence analysis method includes a fluorescence off mode and a fluorescence on mode. The mode based on fluorescence on or enhancement has better immunity to background signals than the fluorescence off mode, so its sensitivity is higher. The metal organic framework Zn-TCPE is a metal Zn2+And ligand H4TCPE is a 2D porous crystal material with a periodic network structure formed by covalent bond self-assembly. The Zn-TCPE has obvious fluorescence property because the ligand has aggregation-induced emission property. However, Zn-TCPE has poor water stability, and Zn is in aqueous solution2+And the cleavage of the carboxyl bond on the ligand, resulting in the rotation of the benzene ring on the ligand and torsional vibration of the carbon-carbon double bond, and thus fluorescence is attenuated. And when the Zn-TCPE crystal material is completely disintegrated, the ligand is completely released to form an aggregate, so that the fluorescence is enhanced. The mode of firstly weakening fluorescence and then strengthening fluorescence is the same as the fluorescence opening mode, and has higher sensitivity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an aminoglycoside antibiotic detection method based on a fluorescent metal organic framework material.
The purpose of the invention is realized by the following scheme: a method for detecting aminoglycoside antibiotics based on a fluorescent metal organic framework material is characterized in that based on the water instability of the fluorescent metal organic framework material and the competitive coordination effect of aminoglycoside antibiotics on metal ions, the structure of the metal organic framework material is promoted to be gradually disintegrated, and the content of aminoglycoside antibiotics is measured through the signal change of firstly weakening fluorescence and then strengthening the fluorescence, and the method comprises the following steps:
(1) preparing a fluorescent metal organic framework material aqueous solution:
weighing a certain mass of fluorescent metal organic framework material, dissolving the fluorescent metal organic framework material in deionized water, and standing the solution at room temperature for a period of time;
(2) fluorescence detection and standard curve drawing of aminoglycoside antibiotics:
weighing a certain mass of standard aminoglycoside antibiotics (tobramycin, gentamicin sulfate and kanamycin sulfate) and dissolving in deionized water to obtain 0.5-10mM aminoglycoside antibiotic solution; opening a fluorescence spectrophotometer, setting the excitation wavelength to be 370nm, the excitation and emission slit to be 5nm, the voltage to be 700V, taking 1mL of aqueous solution of the fluorescent metal organic framework material in a cuvette, and measuring the fluorescence value at 475nm, namely the blank fluorescence value I0(ii) a Sequentially adding 1 μ L aminoglycoside antibiotic solution, mixing, and measuring fluorescence value at 475nm, i.e. fluorescence value I;
drawing a corresponding linear relation curve according to the relation between the fluorescence value ratio and the concentration of the added aminoglycoside antibiotics;
(3) and (3) actual sample detection: and (3) calculating a corresponding fluorescence value ratio by operating the water sample containing the aminoglycoside antibiotics (tobramycin, gentamicin sulfate and kanamycin sulfate) in the step (2), and then substituting the fluorescence value ratio into a standard curve to calculate the corresponding aminoglycoside antibiotic concentration in the actual sample.
On the basis of the scheme, the fluorescent metal organic framework material in the step (1) is selected from water-instable fluorescent Zn-TCPE and a ligand H thereof4TCPE has aggregation-induced emission properties.
On the basis of the scheme, the concentration of the aqueous solution of the fluorescent metal organic framework material in the step (1) is 1 mg/mL.
On the basis of the scheme, the fluorescence value of the aqueous solution of the fluorescent metal organic framework material in the step (1) is hardly changed after standing for 3 hours at room temperature.
Based on the above protocol, the concentrations of aminoglycoside antibiotics in step (2) were 0.5mM, 1mM, 2mM, 3mM, 4mM, 5mM, 6mM, 7mM, 8mM, 9mM, and 10mM, respectively.
On the basis of the scheme, the fluorescence ratio in the step (2) and the step (3) is a fluorescence value I after the aminoglycoside antibiotic is added and a blank fluorescence value I0Ratio of (I)/(I)0。
On the basis of the scheme, the concentration of the aminoglycoside antibiotics in the step (3) is specifically 2 μ M, 4 μ M and 6 μ M.
The principle of the invention is to utilize the water instability of fluorescent Zn-TCPE, Zn in aqueous solution2+And the coordination with carboxyl on the ligand is weakened, even the bond is broken, so that the benzene ring and the carbon-carbon double bond on the ligand are distorted and vibrated, and the fluorescence is weakened. When aminoglycoside antibiotics are added, the amino group of aminoglycoside antibiotics is linked with Zn2+Coordination, resulting in complete disintegration of the Zn-TCPE structure, ligand H4TCPE is released and aggregates occur, and fluorescence is enhanced.
The invention has the advantages that:
(1) the method is realized by utilizing the inherent fluorescent characteristic and chemical property of Zn-TCPE without other fluorescent molecules. Zn in aqueous solution due to the water instability of fluorescent Zn-TCPE2+The coordination with the carboxyl on the ligand is weakened, even the bond is broken, thereby leading to the obvious weakening of fluorescence and achieving the stability after 3 hours.
(2) Simple operation, quick response and high sensitivity. When aminoglycoside antibiotics are added into the Zn-TCPE aqueous solution, abundant amino groups on the molecules can be matched with Zn in the Zn-TCPE2+Coordination, ligand is released immediately, and fluorescence is obviously enhanced.
Drawings
FIG. 1 is an SEM photograph and a fluorescence microscope photograph of Zn-TCPE in example 1 before addition to an aqueous solution;
FIG. 2 is an SEM photograph and a fluorescence microscope photograph of Zn-TCPE in example 1 after addition of an aqueous solution;
FIG. 3 is a fluorescence intensity-time spectrum of an aqueous solution of Zn-TCPE in example 1;
FIG. 4 is a graph of the fluorescence response and standard curve of the aqueous Zn-TCPE solution and tobramycin of example 2;
FIG. 5 is a diagram showing the filter paper irradiated with UV light in example 2;
FIG. 6 is an SEM photograph and a fluorescence microscope photograph of Zn-TCPE after reaction with tobramycin in example 2;
FIG. 7 shows Zn-TCPE and Zn-TCPE + H in example 22O、H4FTIR patterns of TCPE, Tobramycin (TOB) and Zn-TCPE after reaction with tobramycin (Zn-TCPE + TOB);
FIG. 8 is an ESI source mass spectrum of Zn-TCPE reacted with tobramycin in example 2 (Zn-TCPE + TOB);
FIG. 9 shows Zn-TCPE and Zn-TCPE + H in example 22O、H4Nuclear magnetic resonance hydrogen spectrogram of (Zn-TCPE + TOB) after TCPE, Tobramycin (TOB) and Zn-TCPE react with tobramycin;
FIG. 10 is a graph of the fluorescence response and standard curve of the aqueous Zn-TCPE solution and gentamicin sulfate in example 3;
FIG. 11 is a graph showing the fluorescent response of the Zn-TCPE aqueous solution to kanamycin sulfate in example 4 and a standard curve;
FIG. 12 is a graph showing the fluorescence response of the aqueous Zn-TCPE solution of example 5 with different kinds of antibiotics;
FIG. 13 is a graph showing the anti-interference effect of the aqueous Zn-TCPE solution against aminoglycoside antibiotics in example 6.
The technical solution of the present invention is further described below by specific examples. The following examples are further illustrative of the present invention and do not limit the scope of the present invention.
EXAMPLE 1 preparation of an aqueous Zn-TCPE solution
5mg of Zn-TCPE is weighed and dissolved in 5mL of deionized water to obtain 1mg/mL of Zn-TCPE aqueous solution, and the aqueous solution is stored at room temperature in a dark place. SEM pictures and fluorescence microscope pictures before the Zn-TCPE is added into the aqueous solution are shown in figure 1, and SEM pictures and fluorescence microscope pictures after the Zn-TCPE is added into the aqueous solution are shown in figure 2, which proves that the crystal structure of the Zn-TCPE is cracked and the fluorescence is weakened in the aqueous solution. The fluorescence stability of the aqueous Zn-TCPE solution after standing for 3h is shown in FIG. 3.
EXAMPLE 2 Tobramycin concentration Standard Curve
Weighing a certain mass of tobramycin standard substance, and dissolving in deionized water to obtain a 0.5-10mM tobramycin solution. Opening a fluorescence spectrophotometer, setting the excitation wavelength to be 370nm, the excitation and emission slit to be 5nm, the voltage to be 700V, putting 1mL of Zn-TCPE water solution into a cuvette, measuring the fluorescence value, and recording as a blank fluorescence value I0. Then, 1. mu.L of tobramycin solution was added thereto, mixed well, and the fluorescence value was measured and recorded as fluorescence value I.
The corresponding standard curve was fitted to the fluorescence spectra measured by the spectrofluorometer, as shown in FIG. 4. The fluorescence value ratio increases with increasing tobramycin concentration, and the linear regression equation is that y is 0.5038x +0.9716, R20.9991 where y represents the fluorescence value after tobramycin addition I and the blank fluorescence value I0X represents the tobramycin concentration (. mu.M), the limit of detection of this method is 23.8 nM.
To verify the visual detection of the reaction, the filter paper was immersed in the solution after the reaction of the aqueous solution of Zn-TCPE and tobramycin of different concentrations, dried and irradiated with an ultraviolet lamp (365nm), as shown in FIG. 5. The SEM picture and the fluorescence microscopic picture of the Zn-TCPE after the reaction with the tobramycin are shown in figure 6, and the FTIR picture of figure 7, the ESI source mass spectrum of figure 8 and the nuclear magnetic resonance hydrogen spectrum of figure 9 prove that the structure of the Zn-TCPE is completely disintegrated after the reaction with the tobramycin, the ligand is released and the fluorescence is enhanced.
Example 3 drawing of a standard curve for gentamicin sulfate concentration
A certain mass of gentamicin sulfate standard substance is weighed and dissolved in deionized water to obtain 0.5-10mM gentamicin sulfate solution. Opening a fluorescence spectrophotometer, setting the excitation wavelength to be 370nm, the excitation and emission slit to be 5nm, the voltage to be 700V, putting 1mL of Zn-TCPE water solution into a cuvette, measuring the fluorescence value, and recording as a blank fluorescence value I0. Then, 1. mu.L of gentamicin sulfate solution was added, mixed well, and the fluorescence value was measured and recorded as fluorescence value I.
The corresponding standard curve was fitted to the fluorescence spectrum measured by the spectrofluorometer, as shown in FIG. 10. The fluorescence value ratio increases with the concentration of gentamicin sulfate, and the linear regression equation is that y is 0.3213x +0.9939, R20.9973, wherein y represents the fluorescence value I after adding gentamicin sulfate and the blank fluorescence value I0X represents gentamicin sulfate concentration (μ M), the detection limit of this method is 37.3 nM.
EXAMPLE 4 Standard Curve for kanamycin sulfate concentration
Weighing a certain mass of kanamycin sulfate standard substance, and dissolving the kanamycin sulfate standard substance in deionized water to obtain a 0.5-10mM kanamycin sulfate solution. Opening a fluorescence spectrophotometer, setting the excitation wavelength to be 370nm, the excitation and emission slit to be 5nm, the voltage to be 700V, putting 1mL of Zn-TCPE water solution into a cuvette, measuring the fluorescence value, and recording as a blank fluorescence value I0. Subsequently, 1. mu.L of kanamycin sulfate solution was added, mixed well, and the fluorescence value was measured and recorded as fluorescence value I.
The corresponding standard curve was fitted to the fluorescence spectrum measured by the spectrofluorometer, as shown in FIG. 11. The ratio of fluorescence values increased with increasing kanamycin sulfate concentration, and the linear regression equation was that y is 0.2362x +0.7898, R20.9949, wherein y represents the fluorescence value I after addition of kanamycin sulfate and the blank fluorescence value I0X represents the kanamycin sulfate concentration (. mu.M), and the detection limit of this method is 50.8 nM.
Example 5 fluorescent response of aqueous Zn-TCPE solutions with different classes of antibiotics
Preparing different antibiotic solutions (tobramycin, gentamicin sulfate, kanamycin sulfate, tetracycline, chloramphenicol, amoxicillin, erythromycin, aztreonam, nitrofurantoin and furazoline) with the concentration of 1-10 mM. Opening a fluorescence spectrophotometer, setting the excitation wavelength to be 370nm, the excitation and emission slit to be 5nm, the voltage to be 700V, putting 1mL of Zn-TCPE water solution into a cuvette, measuring the fluorescence value, and recording as a blank fluorescence value I0. Subsequently, 1. mu.L of the antibiotic solution was added, mixed well, and the fluorescence value was measured and recorded as fluorescence value I. As shown in FIG. 12, Tubumyces was removedBesides the fluorescence enhancement of the Zn-TCPE aqueous solution caused by the antibiotic, the gentamicin sulfate and the kanamycin sulfate, the fluorescence change of the Zn-TCPE aqueous solution hardly caused by the other antibiotics.
Example 6 anti-interference of aqueous Zn-TCPE solutions with aminoglycoside antibiotics
Preparing different antibiotic solutions (tobramycin, gentamicin sulfate, kanamycin sulfate, tetracycline, chloramphenicol, amoxicillin, erythromycin, aztreonam, nitrofurantoin and furazoline) with the concentration of 1-10 mM. Opening a fluorescence spectrophotometer, setting the excitation wavelength to be 370nm, the excitation and emission slit to be 5nm and the voltage to be 700V, putting 1mL of Zn-TCPE aqueous solution into a cuvette, and measuring the fluorescence value; then, equal amounts of the other antibiotics and aminoglycoside antibiotics were added sequentially to determine the fluorescence values, as shown in FIG. 13.
Example 7 determination of Tobramycin content in actual Water sample
To further verify the accuracy of the method in determining the tobramycin content of the actual samples, a solution of tobramycin (2mM, 4mM, 6mM) was prepared in tap water without pretreatment as a solvent. Opening a fluorescence spectrophotometer, setting the excitation wavelength to be 370nm, the excitation and emission slit to be 5nm, the voltage to be 700V, putting 1mL of 1mg/mL Zn-TCPE aqueous solution prepared by using tap water as a solvent into a cuvette, measuring the fluorescence value, and marking as I0. Then 1. mu.L of tobramycin solution was added, mixed well and the fluorescence value was determined and recorded as I. Finally, the ratio of fluorescence values I/I0Substituting the standard curve to calculate the tobramycin concentration of the actual sample.
Specific samples and test results are shown in table 1.
TABLE 1
Example 8 determination of gentamicin sulfate content in actual Water sample
In order to further verify the accuracy of the method in the determination of the gentamicin sulfate content in the actual sample, tap water without pretreatment is used as a solvent for preparationGentamicin sulfate solution (2mM, 4mM, 6mM) was prepared. Opening a fluorescence spectrophotometer, setting the excitation wavelength to be 370nm, the excitation and emission slit to be 5nm, the voltage to be 700V, putting 1mL of 1mg/mL Zn-TCPE aqueous solution prepared by using tap water as a solvent into a cuvette, measuring the fluorescence value, and marking as I0. Then, 1. mu.L of gentamicin sulfate solution was added, mixed well, and the fluorescence value was measured and recorded as I. Finally, the ratio of fluorescence values I/I0Substituting the standard curve to calculate the concentration of gentamicin sulfate in the actual sample.
Specific samples and test results are shown in table 2.
TABLE 2
Example 9 determination of kanamycin sulfate content in actual Water sample
To further verify the accuracy of this method in determining kanamycin sulfate content in real samples, kanamycin sulfate solution (2mM, 4mM, 6mM) was prepared using tap water without pretreatment as a solvent. Opening a fluorescence spectrophotometer, setting the excitation wavelength to be 370nm, the excitation and emission slit to be 5nm, the voltage to be 700V, putting 1mL of 1mg/mL Zn-TCPE aqueous solution prepared by using tap water as a solvent into a cuvette, measuring the fluorescence value, and marking as I0. Subsequently, 1. mu.L kanamycin sulfate solution was added, mixed well and the fluorescence value was determined as I. Finally, the ratio of fluorescence values I/I0Substituting into the standard curve to calculate the concentration of kanamycin sulfate in the actual sample.
Specific samples and test results are shown in table 3.
TABLE 3
Claims (7)
1. A method for detecting aminoglycoside antibiotics based on a fluorescent metal organic framework material is characterized in that based on the water instability of the fluorescent metal organic framework material and the competitive coordination effect of amino functional groups in aminoglycoside antibiotics on metal ions, the structure of the metal organic framework material is promoted to be gradually disintegrated, and the aminoglycoside antibiotics are detected through the signal change of firstly weakening fluorescence and then strengthening the fluorescence, and the method comprises the following steps:
(1) preparing a fluorescent metal organic framework material aqueous solution:
weighing a certain mass of fluorescent metal organic framework material, dissolving the fluorescent metal organic framework material in deionized water, and standing the solution at room temperature for a period of time;
(2) fluorescence detection and standard curve drawing of aminoglycoside antibiotics:
weighing a certain mass of standard aminoglycoside antibiotics (tobramycin, gentamicin sulfate and kanamycin sulfate) and dissolving in deionized water to obtain 0.5-10mM aminoglycoside antibiotic solution; opening a fluorescence spectrophotometer, setting the excitation wavelength to be 370nm, the excitation and emission slit to be 5nm, the voltage to be 700V, putting 1mL of aqueous solution of the fluorescent metal organic framework material in a cuvette, measuring the fluorescence value, and recording as a blank fluorescence value I0(ii) a Sequentially adding 1 mu L of aminoglycoside antibiotic solution, uniformly mixing, and measuring the fluorescence value which is recorded as fluorescence value I;
drawing a corresponding linear relation curve according to the relation between the fluorescence value ratio and the concentration of the added aminoglycoside antibiotics;
(3) and (3) actual sample detection: and (3) calculating a corresponding fluorescence value ratio by operating the water sample containing the aminoglycoside antibiotics (tobramycin, gentamicin sulfate and kanamycin sulfate) in the step (2), and then substituting the fluorescence value ratio into a standard curve to calculate the corresponding aminoglycoside antibiotic concentration in the actual sample.
2. The method for detecting aminoglycoside antibiotics based on fluorescent metal organic framework material according to claim 1, wherein: the fluorescent metal organic framework material in the step (1) is selected from water-unstable fluorescent Zn-TCPE and ligand H thereof4TCPE has aggregation-induced emission properties.
3. The method for detecting aminoglycoside antibiotics based on fluorescent metal organic framework material according to claim 1, wherein: the concentration of the aqueous solution of the fluorescent metal organic framework material in the step (1) is 1 mg/mL.
4. The method for detecting aminoglycoside antibiotics based on fluorescent metal organic framework material according to claim 1, wherein: and (2) after the aqueous solution of the fluorescent metal organic framework material in the step (1) is kept still at room temperature for 3 hours, the fluorescence value is almost not changed.
5. The method for detecting aminoglycoside antibiotics based on fluorescent metal organic framework material according to claim 1, wherein: the aminoglycoside antibiotic concentration was 0.5mM, 1mM, 2mM, 3mM, 4mM, 5mM, 6mM, 7mM, 8mM, 9mM, 10mM, respectively.
6. The method for detecting aminoglycoside antibiotics based on fluorescent metal organic framework material according to claim 1, wherein: the fluorescence ratio in the step (2) and the step (3) is a fluorescence value I after the aminoglycoside antibiotics are added and a blank fluorescence value I0Ratio of (I)/(I)0。
7. The method for detecting aminoglycoside antibiotics based on fluorescent metal organic framework material according to claim 1, wherein: the concentration of the aminoglycoside antibiotics in the step (3) is specifically 2 μ M, 4 μ M and 6 μ M.
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