mSiO2-COOH-rare earth ion complex probe and its application in visual detection of antibiotics

Abstract

The present invention discloses a porous silica-rare earth ion complex probe with surface carboxylic acid functionalization, which can be used for adsorption-induced fluorescence enhancement test paper for antibiotic detection. The test paper is a porous silica with a high surface area modified on the surface of ordinary filter paper. After the surface carboxylic acid of the silica is functionalized, the adsorbed rare earth ions have different coordination abilities with different antibiotics, so that the rare earth fluorescence signal is enhanced to varying degrees after the action, thereby realizing the semi-quantitative detection of multiple antibiotics based on color and chromaticity changes. The adsorption-induced fluorescence enhancement test paper prepared by the present invention has the advantages of simple preparation method, long storage time, easy to carry, easy to operate, etc., which can solve the technical problems of single target, insufficient sensitivity and complex detection process of existing antibiotic detection, and has remarkable detection effect in actual samples, which is helpful for on-site detection of multiple antibiotics in actual samples.

Description

Technical Field

[0001] The invention relates to the field of food safety detection, and in particular to a method for preparing and using a fluorescent test strip for detecting antibiotics such as norfloxacin, gatifloxacin and oxytetracycline in milk or meat products. Background Art

[0002] With the development and progress of science and technology, antibiotics are widely used in agriculture, animal husbandry, aquaculture, and other related industries. Therefore, as an emerging pollutant, it has the potential risk of remaining in soil, water, agricultural products, etc. Once the residue is excessive, it will endanger people's health and the safety of the ecological environment through the food chain and ecological cycle. Therefore, how to achieve rapid and accurate detection of antibiotics has become the focus of people's attention.

[0003] Based on the above research objectives, we designed and synthesized adsorption-induced fluorescence enhancement test paper for the detection of multiple antibiotics. The test paper is made of porous silica with a high surface area modified on the surface of ordinary filter paper. After the surface of silica is functionalized with carboxylic acid, the adsorbed rare earth ions (Tb 3+ 、Eu 3+ ,La 3+ ) and norfloxacin NFX, gatifloxacin GTA, oxytetracycline OTC have different coordination abilities, so that the rare earth fluorescence signal is enhanced to different degrees after the action, thereby realizing the semi-quantitative detection of multiple antibiotics based on color and chromaticity changes. The adsorption-induced fluorescence enhancement test paper prepared by the present invention has the advantages of simple preparation method, long storage time, easy to carry, easy to operate, etc., which can solve the technical problems of single target, insufficient sensitivity and complex detection process of existing antibiotic detection, and is helpful for the real sample detection of multiple antibiotics. Summary of the invention

[0004] The purpose of the present invention is to provide a surface carboxylic acid functionalized porous silica-rare earth ion composite probe to address the deficiencies of the prior art. The composite probe can realize visual detection of multiple antibiotic molecules according to the different coordination effects between rare earth ions and antibiotics, and has high selectivity and good sensitivity.

[0005] In order to achieve the above purpose, the technical solution of the present invention is:

[0006] (1) Preparation of porous silicon dioxide mSiO2:

[0007] (2) Preparation of porous silica mSiO2-COOH functionalized with surface carboxylic acid:

[0008] (3) Preparation of porous silica-rare earth ion composite probe mSiO2-COOH@RE functionalized with surface carboxylic acid, where RE can be Tb 3+ 、Eu 3+,La 3+ wait.

[0009] Specifically, the present invention can be implemented by the following technical solutions:

[0010] 1) Synthesis of porous silica and its surface functionalization with carboxylic acid

[0011] Dissolve 10-100 mg of triethanolamine in 5-100 mL of ultrapure water, and stir the mixture at a suitable speed for 10-60 min in a high-temperature oil bath (90°C-120°C). Then add 50-500 mg of hexadecyltrimethylammonium bromide and 30-300 mg of sodium salicylate to the reaction system, continue the reaction for 60-300 min, then add 1-10 mL of TEOS (ethyl silicate), and continue the reaction at the same speed for 60-300 min. After the reaction is completed, the obtained product is centrifuged and washed, and the obtained product is dispersed in a mixed solution of methanol and hydrochloric acid (volume ratio 1:1-1:20) under the condition of a high-temperature oil bath and refluxed for 5-15 h to remove the residual template. The above reflux process is repeated 3-5 times, and the mixture is dispersed in anhydrous ethanol after centrifugal washing several times to obtain porous silica with a high surface area. In order to improve the adsorption capacity of -COOH group on mSiO2, we first modified the amino group on the prepared mSiO2; added 1-10mL APTES ((3-aminopropyl) triethoxysilane) to the above product dispersed in ethanol, stirred and reacted at room temperature for 5-24h, centrifuged and washed the product, and dispersed it in anhydrous ethanol. Then, 0.01-0.5mol of succinic anhydride and 0.01-0.5mol of 4-lutidine were added to the above system, stirred and reacted at room temperature for 10-24h. After centrifugation and washing 3-5 times, the obtained product was dispersed in anhydrous ethanol to obtain porous silica with high surface area modified with carboxylic acid groups.

[0012] 2) Construction of surface carboxylic acid functionalized porous silica-rare earth ion complex probe

[0013] Configure 0.01~0.5mol / L Tb 3+ 、Eu 3+ ,La 3+ Then, 10-20 mL of the prepared mSiO2-COOH was taken and stirred with the above ion solution at room temperature for 10-24 h, and the product was centrifuged and washed 3-5 times to obtain the surface carboxylic acid functionalized porous silica-preferred rare earth ion composite probe, and the composite probe mSiO2-COOH@Tb 3 + ,mSiO2-COOH@Eu 3+ ,mSiO2-COOH@La 3+Freeze-dried for use.

[0014] 3): Preparation of composite probe fluorescent test paper based on microporous filtration membrane

[0015] The microporous filtration membrane (0.22 μm, mixed cellulose ester) was first pretreated with oxygen plasma for 2 to 30 minutes to remove surface impurity molecules. 3+ ,mSiO2-COOH@Eu 3+ ,mSiO2-COOH@La 3+ After ultrasonic treatment for 10 to 30 minutes, the suspension is poured into a cylindrical funnel. Then, it is filtered or vacuum-filtered to adsorb the complex probe in the micropores. The filter membrane is removed, air-dried, and then stored in the dark for the detection of different antibiotic drug molecules.

[0016] In step 1, the flower-like porous SiO2 surface is modified with carboxylic acid groups, which is conducive to the adsorption of the preferred rare earth ions (Tb 3+ 、Eu 3+ ,La 3+ ).

[0017] The composite probe mSiO2-COOH@Tb in step 2 3+ ,mSiO2-COOH@Eu 3+ ,mSiO2-COOH@La 3+ The pH value of the preparation is 6-8.

[0018] In step 3, a matrix material mixed cellulose ester microporous filtration membrane is used, and the micropore size is 0.22 microns.

[0019] In step 3, the composite probe mSiO2-COOH@Tb is adsorbed in the micropores of the mixed cellulose ester microporous filtration membrane by filtration or vacuum filtration. 3+ ,mSiO2-COOH@Eu 3+ ,mSiO2-COOH@La 3+ .

[0020] The single-emission fluorescent test paper described in step 3 is colorless under ultraviolet light, but after combining with different antibiotics, such as norfloxacin, it appears green under ultraviolet light, oxytetracycline, it appears red under ultraviolet light, and gatifloxacin, it appears blue under ultraviolet light.

[0021] After the fluorescent test paper is immersed in the test solution, or the test solution is dripped onto the fluorescent test paper, about 15-25 seconds, and then the fluorescent test paper is irradiated with ultraviolet light. 3+If the fluorescent test paper turns green, it means that the test object contains norfloxacin; if it is modified with mSiO2-COOH@Eu 3+ If the fluorescent test paper turns red, it means that the test substance contains oxytetracycline; if it is modified with mSiO2-COOH@La 3+ If the fluorescent test paper turns blue, it means that the test object contains gatifloxacin. As the concentration of antibiotics increases, the color becomes darker.

[0022] Fluorescent test paper can identify and semi-quantitatively detect norfloxacin, gatifloxacin and oxytetracycline, respectively. The concentration ranges of norfloxacin, gatifloxacin and oxytetracycline are as low as 0.02, 0.02 and 3.5 μmol / L and as high as 50, 45 and 40 μmol / L.

[0023] Fluorescent test paper is used to detect norfloxacin, gatifloxacin and oxytetracycline. The ultraviolet lamp excitation wavelength is 312nm, the pH of the sample solution to be tested is 6.0-8.0, and the reaction temperature is 15-25°C.

[0024] The fluorescent test paper is used to detect norfloxacin, gatifloxacin and oxytetracycline. After the fluorescent test paper is immersed in a standard norfloxacin, gatifloxacin and oxytetracycline solution, or the standard solution is dripped onto the fluorescent test paper and fully reacted, the fluorescent color or chromaticity enhancement degree of the surface carboxylic acid functionalized porous silica-preferably rare earth ion complex probe is observed to achieve visual detection of the antibiotics in the test solution.

[0025] Take a small amount of the test substance and add it dropwise to the mSiO2-COOH@Tb 3+ On the fluorescent test paper, if the test paper turns green under ultraviolet light, it means that the test object contains norfloxacin. If the test paper does not change color, it means that the test object does not contain norfloxacin or its content is below the minimum detection limit.

[0026] Take an equal amount of the above test substance and add it dropwise to mSiO2-COOH@Eu 3+ On the fluorescent test paper, if the test paper turns red under ultraviolet light, it means that the test substance contains norfloxacin or oxytetracycline. At this time, take an equal amount of the above test substance and add it dropwise to the mSiO2-COOH@Tb 3+ On the fluorescent test paper, if the test paper turns green under ultraviolet light, it means that the test object contains norfloxacin and oxytetracycline; if the test paper does not change color, it means that the test object does not contain norfloxacin or its content is below the minimum detection limit, and contains oxytetracycline;

[0027] Take an equal amount of the test substance and add it dropwise to the mSiO2-COOH@La 3+ On the fluorescent test paper, if the test paper turns blue, it means that the test object contains gatifloxacin. If the test paper does not change color, it means that the test object does not contain the above-mentioned oxytetracycline or the concentration of the three antibiotics contained is lower than the minimum detection limit of the probe.

[0028] The present invention discloses a method for preparing and using a composite probe fluorescent test paper based on a microporous filter membrane, which is simple and takes a short time. The present invention also provides a method for visually identifying antibiotics such as norfloxacin, gatifloxacin, and oxytetracycline. The identification method only requires the naked eye to detect whether a color change or a change in chromaticity occurs after the fluorescent test paper irradiated with an ultraviolet lamp reacts with a sample to be tested, and the presence of antibiotics such as norfloxacin, gatifloxacin, and oxytetracycline can be determined, thereby realizing the identification and semi-quantitative detection of multiple antibiotics. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1A , Figure 1B , Figure 1C The transmission electron microscope image and element distribution map of the composite probe. In the image, the flower-like structure of the probe can be seen. In c), the C element is black, the Si element is green, the O element is red, and the rare earth element is blue-green.

[0030] Figure 2 mSiO2-COOH@Eu 3+ Fluorescence graph and linear relationship diagram of oxytetracycline OTC gradient detection.

[0031] Figure 3 mSiO2-COOH@Tb 3+ Fluorescence graph and linear relationship diagram of gradient detection of norfloxacin NFX.

[0032] Figure 4 mSiO2-COOH@La 3+ Fluorescence graph and linear relationship diagram of gatifloxacin GTA gradient detection.

[0033] Figure 5 The fluorescence photos of the three probes prepared for the detection of oxytetracycline, gatifloxacin and norfloxacin after mixing two of each other. The detection showed obvious differences in color changes.

[0034] Figure 6 BET data of the prepared probe. The adsorption capacity can reach 600-610m 2 / g. DETAILED DESCRIPTION

[0035] The following embodiments are further descriptions of the content of the present invention as an explanation of the technical content of the present invention, but the essential content of the present invention is not limited to the following embodiments. Ordinary technicians in this field can and should know that any simple changes or replacements based on the essential spirit of the present invention should fall within the scope of protection required by the present invention.

[0036] Example 1

[0037] Step 1: Synthesis of porous silica and surface functionalization with carboxylic acid

[0038] 34 mg of triethanolamine was dissolved in 12.6 mL of ultrapure water and stirred for 30 min in a high temperature oil bath. Then 190 mg of hexadecyltrimethylammonium bromide and 84 mg of sodium salicylate were added to the above reaction system, and the reaction continued for 30 min. Then 2 mL of TEOS was added and the reaction continued for 60 min at the same speed. After the reaction, the obtained product was centrifuged and washed. Under the condition of a high temperature oil bath, the obtained product was dispersed in a mixed solution of methanol and hydrochloric acid (concentration 36%-38%) (volume ratio 1:10) and refluxed for 8 h to remove the residual template. The above reflux process was repeated 3 times, and the product was dispersed in anhydrous ethanol after several centrifugal washings to obtain porous silica with high surface area. In order to improve the adsorption capacity of -COOH group on mSiO2, we first modified the amino group on the prepared mSiO2; 2 mL of APTES was added to the above product dispersed in ethanol, and the reaction was stirred for 10 h at room temperature. The product was centrifuged and washed, and then dispersed in anhydrous ethanol. Then, 0.1 mol of succinic anhydride and 0.1 mol of 4-lutidine were added to the above system and stirred at room temperature for 24 hours. The obtained product was centrifuged and washed three times, and then dispersed in anhydrous ethanol to obtain porous silica with a high surface area modified with carboxylic acid groups.

[0039] Step 2: Construction of surface carboxylic acid functionalized porous silica-preferred rare earth ion complex probe

[0040] Configure 0.1mol / L Tb 3+ Then, 15 mL of the prepared mSiO2-COOH was taken and stirred with the above ion solution at room temperature for 24 h, and the product was centrifuged and washed three times to obtain the surface carboxylic acid functionalized porous silica-preferred rare earth ion composite probe, and the composite probe mSiO2-COOH@Tb 3+ , freeze-dried for later use.

[0041] Step 3: Preparation of complex probe fluorescent test paper based on microporous filtration membrane

[0042] The microporous filtration membrane (0.22 μm, mixed cellulose ester) was first pretreated with oxygen plasma cleaning for 8 minutes to remove surface impurity molecules. 3+ After 10 minutes of ultrasonic treatment, the suspension was poured into a cylindrical funnel. Then, the complex probe was adsorbed in the micropores by filtration or vacuum filtration. The filter membrane was removed, air-dried, and then stored in the dark for the detection of norfloxacin.

[0043] Example 2

[0044] Step 1: Synthesis of high surface area porous silica and its surface functionalization with carboxylic acid

[0045] 17 mg of triethanolamine was dissolved in 6.3 mL of ultrapure water and stirred for 15 min in a high temperature oil bath. Then 95 mg of hexadecyltrimethylammonium bromide and 42 mg of sodium salicylate were added to the above reaction system, and the reaction was continued for 30 min. Then 1 mL of TEOS was added and the reaction was continued for 60 min at the same speed. After the reaction, the obtained product was centrifuged and washed. Under the condition of a high temperature oil bath, the obtained product was dispersed in a mixed solution of methanol and hydrochloric acid (volume ratio 1:5) and refluxed for 5 h to remove the residual template. The above reflux process was repeated 3 times, and the product was dispersed in anhydrous ethanol after several centrifugal washings to obtain porous silica with high surface area. In order to improve the adsorption capacity of -COOH group on mSiO2, we first modified the amino group on the prepared mSiO2; 1 mL of APTES was added to the above product dispersed in ethanol, and the reaction was stirred for 10 h at room temperature. The product was centrifuged and washed, and then dispersed in anhydrous ethanol. Then, 0.05 mol of succinic anhydride and 0.05 mol of 4-lutidine were added to the above system and stirred at room temperature for 18 hours. The obtained product was centrifuged and washed three times, and then dispersed in anhydrous ethanol to obtain porous silica with a high surface area modified with carboxylic acid groups.

[0046] Step 2: Construction of surface carboxylic acid functionalized porous silica-preferred rare earth ion complex probe

[0047] Prepare 0.05 mol / L Eu 3+ Then, 10 mL of the prepared mSiO2-COOH was taken and reacted with the above ion solution at room temperature for 18 h, and the product was centrifuged and washed 3 times to obtain the surface carboxylic acid functionalized porous silica-preferred rare earth ion complex probe. The complex probe mSiO2-COOH@Eu 3+ , freeze-dried for later use.

[0048] Step 3: Preparation of complex probe fluorescent test paper based on microporous filtration membrane

[0049] The microporous filtration membrane (0.22 μm, mixed cellulose ester) was first pretreated with oxygen plasma for 2 to 30 minutes to remove surface impurity molecules. 3+ After 10 minutes of ultrasonic treatment, the suspension was poured into a cylindrical funnel. Then, the complex probe was adsorbed in the micropores by filtration or vacuum filtration. The filter membrane was removed, air-dried, and then stored in the dark for the detection of oxytetracycline.

[0050] Example 3

[0051] Step 1: Synthesis of high surface area porous silica and its surface functionalization with carboxylic acid

[0052] 85 mg of triethanolamine was dissolved in 31.5 mL of ultrapure water and stirred for 40 min in a high temperature oil bath. Then 475 mg of hexadecyltrimethylammonium bromide and 210 mg of sodium salicylate were added to the above reaction system, and the reaction continued for 40 min. Then 5 mL of TEOS was added and the reaction continued for 80 min at the same speed. After the reaction, the obtained product was centrifuged and washed. Under the condition of a high temperature oil bath, the obtained product was dispersed in a mixed solution of methanol and hydrochloric acid (volume ratio 1:15) and refluxed for 8 h to remove the residual template. The above reflux process was repeated 3 times, and the product was dispersed in anhydrous ethanol after several centrifugal washings to obtain porous silica with high surface area. In order to improve the adsorption capacity of -COOH group on mSiO2, we first modified the amino group on the prepared mSiO2; 5 mL of APTES was added to the above product dispersed in ethanol, and the reaction was stirred for 18 h at room temperature. The product was centrifuged and washed, and then dispersed in anhydrous ethanol. Then, 0.25 mol of succinic anhydride and 0.25 mol of 4-lutidine were added to the above system and stirred at room temperature for 24 hours. The obtained product was centrifuged and washed three times, and then dispersed in anhydrous ethanol to obtain porous silica with a high surface area modified with carboxylic acid groups.

[0053] Step 2: Construction of surface carboxylic acid functionalized porous silica-preferred rare earth ion complex probe

[0054] Prepare 0.25 mol / L La 3+ Then, 10 mL of the prepared mSiO2-COOH was taken and reacted with the above ion solution at room temperature for 24 h, and the product was centrifuged and washed three times to obtain the surface carboxylic acid functionalized porous silica-preferred rare earth ion composite probe. The composite probe mSiO2-COOH@La 3+ , freeze-dried for later use.

[0055] Step 3: Preparation of complex probe fluorescent test paper based on microporous filtration membrane

[0056] The microporous filtration membrane (0.22 μm, mixed cellulose ester) was first pretreated with oxygen plasma for 15 min to remove surface impurities. 3+ After 10 minutes of ultrasonic treatment, the suspension was poured into a cylindrical funnel. Then, the complex probe was adsorbed in the micropores by filtration or vacuum filtration. The filter membrane was removed, air-dried, and then stored in the dark for the detection of gatifloxacin.

[0057] Application Examples

[0058] After the fluorescent test paper prepared by the present invention is immersed in the test solution, or the test solution is dripped onto the fluorescent test paper, after about 20 seconds, the fluorescent test paper is irradiated with ultraviolet light. 3+ If the fluorescent test paper turns green, it means that the test object contains norfloxacin; if it is modified with mSiO2-COOH@Eu 3+ If the fluorescent test paper turns red, it means that the test substance contains oxytetracycline; if it is modified with mSiO2-COOH@La 3+ If the fluorescent test paper turns blue, it means that the test object contains gatifloxacin.

[0059] The fluorescent test paper prepared by the present invention can identify and semi-quantitatively detect norfloxacin, gatifloxacin and oxytetracycline, respectively, and the concentration ranges of norfloxacin, gatifloxacin and oxytetracycline are as low as 0.02, 0.02 and 3.5 μmol / L and as high as 50, 45 and 40 μmol / L.

[0060] The fluorescent test paper prepared by the invention is used for detecting norfloxacin, gatifloxacin and oxytetracycline, the ultraviolet lamp excitation wavelength is 312nm, the pH value of the sample solution to be tested is 6.0-8.0, the reaction time is 15-25 seconds, and the reaction temperature is 15-25°C.

[0061] The fluorescent test paper prepared by the present invention is used to detect norfloxacin, gatifloxacin and oxytetracycline. After the fluorescent test paper is immersed in a standard norfloxacin, gatifloxacin and oxytetracycline solution, or the standard solution is dripped onto the fluorescent test paper for sufficient reaction, the fluorescent color or chromaticity enhancement degree of the surface carboxylic acid functionalized porous silica-preferably rare earth ion complex probe is observed to achieve visual detection of the antibiotics in the test solution.

[0062] It should be noted that the above-mentioned technical contents of the present invention are only for explanation and clarification to enable those skilled in the art to understand the technical essence of the present invention, so the technical contents are not used to limit the substantial protection scope of the present invention. The substantial protection scope of the present invention shall be subject to the claims. Those skilled in the art should know that any modification, equivalent substitution and improvement based on the substantial spirit of the present invention shall be within the substantial protection scope of the present invention.

Claims

1. A method for preparing porous silica functionalized with surface carboxylic acid, comprising the following steps: Step (1) Preparation of mSiO2: Dissolve triethanolamine in ultrapure water and react in a high-temperature oil bath for 10 to 60 minutes; add hexadecyltrimethylammonium bromide and sodium salicylate, continue to react for 60 to 300 minutes, and then add TEOS to react for 60 to 300 minutes; centrifuge and wash the obtained product, disperse it in a mixed solution of methanol and hydrochloric acid under the condition of a high-temperature oil bath and reflux it for 5 to 15 hours, disperse it in anhydrous ethanol after centrifugation and washing, and obtain porous silicon dioxide dispersed in anhydrous ethanol, namely mSiO2; Step (2) Preparation of mSiO2-COOH: APTES is added to the product obtained in step (1), and the mixture is stirred at room temperature for 5 to 24 hours, followed by centrifugation and washing, and the product is dispersed in anhydrous ethanol; succinic anhydride and 4-lutidine are added to anhydrous ethanol, and the mixture is stirred at room temperature for 10 to 24 hours; the product is centrifuged and washed, and dispersed in anhydrous ethanol to obtain porous silica functionalized with surface carboxylic acid, i.e., mSiO2-COOH.

2. The method for preparing porous silica functionalized with surface carboxylic acid according to claim 1, characterized in that: Step (1) Dissolve 10-100 mg of triethanolamine in 5-100 mL of ultrapure water; 50-500 mg of hexadecyltrimethylammonium bromide, 30-300 mg of sodium salicylate, and 1-10 mL of TEOS.

3. The method for preparing porous silica functionalized with surface carboxylic acid according to claim 1, characterized in that: In the mixed solution of methanol and hydrochloric acid in step (1), the volume ratio of methanol to hydrochloric acid is 1:1 to 1:

20.

4. The method for preparing porous silica functionalized with surface carboxylic acid according to claim 1, characterized in that: Step (2) The volume ratio of APTES to TEOS is 1-10:1-10; the molar ratio of succinic anhydride to 4-lutidine is 1-10:1-10.

5. The method for preparing porous silica functionalized with surface carboxylic acid according to claim 4, characterized in that: The volume ratio of APTES to TEOS is 1:5 to 1:

5.

6. The method for preparing porous silica functionalized with surface carboxylic acid according to claim 5, characterized in that: The volume ratio of APTES to TEOS is 1:2 to 1:

2.

7. The method for preparing porous silica functionalized with surface carboxylic acid according to claim 4, characterized in that: The molar ratio of succinic anhydride to 4-lutidine is 1:5 to 1:

5.

8. The method for preparing porous silica functionalized with surface carboxylic acid according to claim 7, characterized in that: The molar ratio of succinic anhydride to 4-lutidine is 1:2 to 1:

2.

9. The porous silica functionalized with surface carboxylic acid obtained by the preparation method according to any one of claims 1 to 8, characterized in that: Silica has a flower-like porous structure with a particle size of 70-500nm.

10. A porous silica-rare earth ion complex probe functionalized with surface carboxylic acid, characterized in that: The porous silica material functionalized with surface carboxylic acid as claimed in claim 9 is compounded with rare earth ions.

11. Use of the porous silica-rare earth ion complex probe functionalized with surface carboxylic acid according to claim 10 in the visual detection of antibiotics, characterized in that: By bringing the complex probe system into contact with, compounding or mixing with a sample to be detected containing antibiotics, an obvious color change occurs under ultraviolet light, thereby achieving visual detection of the antibiotics.

12. The use according to claim 11, characterized in that The complex probe system is a solution of the complex probe or a fluorescent test paper of the complex probe.

13. The use according to claim 12, characterized in that The fluorescent test paper of the composite probe is obtained by fixing the composite probe on a matrix material, and the matrix material is a mixed cellulose ester microporous filtration membrane.

14. The use according to claim 13, characterized in that The method comprises the following steps: immersing the fluorescent test paper in a test solution containing the antibiotic, or dripping the test solution onto the fluorescent test paper, and after 15-25 seconds, irradiating the fluorescent test paper with an ultraviolet lamp. If an obvious color change occurs, the antibiotic can be visually detected by naked eyes.

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