Specific detection method for tetracycline antibiotics in water based on fluorescent ionic liquid
By using the fluorescent ionic liquid tetrabutyl(naphthoic acid) phosphorus compound as a fluorescent probe, the problems of long detection time and instability of tetracycline antibiotics in water in the existing technology are solved, and a highly sensitive, rapid and stable specific detection effect is achieved, which is suitable for water quality testing.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SUZHOU UNIV OF SCI & TECH
- Filing Date
- 2026-01-30
- Publication Date
- 2026-04-21
AI Technical Summary
Existing technologies for detecting tetracycline antibiotics in water suffer from problems such as long processing time, instability, and low sensitivity, making it difficult to achieve efficient and specific detection.
Using the fluorescent ionic liquid tetrabutyl(naphthoic acid) phosphorus compound as a fluorescent probe, tetracycline antibiotics in water samples are detected by fluorescence detection. Combined with specific pretreatment steps and fluorescence detection methods, the specific detection of tetracycline antibiotics is achieved.
It achieves highly sensitive, rapid, stable, and accurate specific detection of tetracycline antibiotics in water, with a low detection limit, suitable for complex environments, and has a simple synthesis process that is easy to scale up for production.
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Figure CN121899096A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the preparation of a tetrabutyl(naphthoic acid) phosphorus fluorescent ion, which is suitable for use as a fluorescent probe and can be used as a fluorescent sensor in the field of environmental analysis for the specific detection of tetracycline antibiotics in water quality such as rivers. Background Technology
[0002] Tetracycline antibiotics (TCs) are a class of broad-spectrum antibiotics produced by actinomycetes, primarily used to treat bacterial and pathogenic diseases. TCs are mainly used by humans and livestock, but they are difficult to digest and absorb. Most ingested TCs are converted into more toxic metabolites and excreted into urban sewage through the human body, subsequently entering soil, water bodies, and river sediments. Due to their persistence, TCs are frequently detected in soil, water, and river sediments, and even found in surface water and drinking water. Studies have shown that TCs can disrupt the balance of ecosystems. Therefore, TC antibiotics have been identified as emerging environmental pollutants. Currently, the detection methods for tetracycline antibiotics are mainly based on traditional methods, such as liquid chromatography-mass spectrometry (LC-MS), liquid chromatography, electrochemical techniques, and colorimetric analysis. These methods are often time-consuming or unstable. This paper, for the first time, proposes a method for the specific detection of tetracycline antibiotics in water based on fluorescent ionic liquids. This method features convenient operation, high sensitivity, short response time, low detection limit, good stability, and high accuracy. Summary of the Invention
[0003] The purpose of this invention is to propose a method for detecting tetracycline pollutants in water based on fluorescent ionic liquids. This invention is applicable to the detection of tetracycline antibiotics when water contains different types of ions and other types of antibiotics, and has very high application value and development prospects.
[0004] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:
[0005] A method for the specific detection of tetracycline antibiotics in water based on fluorescent ionic liquids includes the following steps: pretreatment of the water sample, adding tetrabutyl(naphthoic acid) phosphorus fluorescent ionic liquid to the pretreated water sample containing tetracycline antibiotics, and performing fluorescence detection immediately; wherein the anion of the fluorescent ionic liquid contains a naphthalene ring structure.
[0006] In this invention, the structure of the fluorescent ionic liquid is as follows:
[0007]
[0008] TC (tetracycline), CTC (chlortetracycline), MTC (methoxycycline), MOC (methoxycycline), DOX (doxycycline), OTC (oxycycline), cations, such as Zr 3+ Ni + Na + Mn 2+ Li + K + Fe 3+ Fe 2+ Cu 2+ Bi + Sn 2+ Pb 2+ Co + Ag + Anions, such as NO3. - Cl - Other sulfonamide antibiotics, such as sulfadiazine, sulfamethoxypyrimidine, sulfamethoxazole, sulfadiazine, and other quinolone antibiotics, such as NOR (norfloxacin), FLE (fluroxacin), and GIP (ciprofloxacin).
[0009] In this invention, the pretreatment of the water sample includes centrifugation for 5 minutes, taking the supernatant, and filtering it through a 0.45-μm membrane filter.
[0010] In this invention, the ratio of fluorescent ionic liquid to the water being tested is 200 μL: 1600 μL; the concentration of the fluorescent ionic liquid is 10 mmol / L; and the concentration of the tetracycline antibiotic is 1-200 μmol / L.
[0011] In this invention, the pH of the water is 2-12, preferably pH=4.
[0012] To achieve the above-mentioned objectives, the fluorescent ionic liquid involved in this invention employs the following preparation method:
[0013] (1) Weigh 0.8 g of sodium hydroxide (20 mmol) into a beaker, add 6.7 mL of distilled water and shake well to prepare a 3 mol / L sodium hydroxide solution as a solvent. Transfer the prepared solution to a three-necked flask for later use. Weigh 3.344 g (19.42 mmol) of 1-naphthoic acid and add it to the prepared sodium hydroxide solution (slight excess sodium hydroxide is added here to ensure the reaction proceeds fully; the specific ratio is: the molar ratio of sodium hydroxide to 1-naphthoic acid is 1.03:1). The system is stirred at 30 ℃ for 24 h in a constant temperature magnetic stirrer. The final product is a yellow liquid.
[0014] (2) Add all of the sodium 1-naphthoate solution generated in the first step to a three-necked flask. Measure 4.27 mL of a 4.53 mol / L tetrabutylphosphine bromide (TPAH) aqueous solution (19.42 mmol) and add it to a 250 mL three-necked flask. Use nitrogen as a protective gas to purge the air from the flask. Seal with a glass stopper. The system is reacted overnight at 40 °C using a magnetic stirrer under constant temperature. After concentrating the supernatant, add 20 mL of anhydrous ethanol and let stand overnight. After filtration, rotary evaporation, and vacuum drying, the target product is obtained as an orange-yellow viscous liquid with a yield of 86.3%.
[0015] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0016] ①This invention utilizes fluorescent ionic liquid compounds to detect tetracycline-class antibiotics.
[0017] ②This invention utilizes fluorescent ionic liquid compounds to detect tetracycline antibiotics in water at a low limit of 1.5 μmol / L.
[0018] ③This invention is a specific detection method that can achieve specific detection of tetracycline antibiotics in water bodies under complex environments.
[0019] ④ This invention provides a specific detection method for tetracycline antibiotics in water based on fluorescent ionic liquids, which features convenient operation, high sensitivity, short response time, good stability, and high accuracy.
[0020] ⑤ The synthesis process of the fluorescent ionic liquid tetrabutyl(naphthoic acid) phosphorus of the present invention is simple and easy to scale up. Attached Figure Description
[0021] The following diagram is provided to further illustrate the structure and performance of the product.
[0022] Figure 1 NMR spectrum of tetrabutyl(naphthoic acid) phosphate ionic liquid.
[0023] Figure 2 Fluorescence quenching of tetrabutyl (naphthoic acid) phosphate ionic liquid at different pH values.
[0024] Figure 3 It is a fluorescent ionic liquid for the specific detection of tetracycline antibiotics when multiple antibiotics and ions are mixed in the water. Detailed Implementation
[0025] To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the following examples provide a more detailed description of the invention. It should be noted that the specific embodiments described herein are merely illustrative and not intended to limit the scope of the invention.
[0026] Preparation Example
[0027]
[0028]
[0029] Weigh 0.8 g (20 mmol) of sodium hydroxide into a beaker, add 6.7 mL of distilled water, and shake well to prepare a 3 mol / L sodium hydroxide solution as the solvent. Transfer the prepared solution to a three-necked flask for later use. Weigh 3.344 g (19.42 mmol) of 1-naphthoic acid and add it to the prepared sodium hydroxide solution (slight excess sodium hydroxide is used here to ensure complete reaction; the specific ratio is: molar ratio of sodium hydroxide to 1-naphthoic acid is 1.03:1). The system is stirred at 30 °C for 24 h in a magnetic stirrer under constant temperature. The final product is a yellow liquid.
[0030] The sodium 1-naphthoate solution generated in the first step was completely added to a three-necked flask. 4.27 mL of a 4.53 mol / L tetrabutylphosphine bromide (TPAH) aqueous solution (19.42 mmol) was measured and added to a 250 mL three-necked flask. Nitrogen gas was used as a protective gas to purge the air from the flask. The flask was sealed with a glass stopper. The system was reacted overnight at 40 °C using a magnetic stirrer under constant temperature. The supernatant was concentrated, and 20 mL of anhydrous ethanol was added. The mixture was allowed to stand overnight. After filtration, rotary evaporation, and vacuum drying, the target product was obtained as an orange-yellow viscous liquid with a yield of 86.3%. Figures 1-3 As shown, Figure 1 NMR spectrum of tetrabutyl(naphthoic acid) phosphate ionic liquid. Figure 2 Fluorescence quenching of tetrabutyl (naphthoic acid) phosphate ionic liquid at different pH values. Figure 3 It is a fluorescent ionic liquid for the specific detection of tetracycline antibiotics when multiple antibiotics and ions are mixed in the water.
[0031] Fluorescence test example
[0032] Example 1
[0033] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of an ethanol-water solution, and the pH was adjusted to 2. The performance of the solution was tested using a fluorescence spectrometer. The measured ΔF, the difference between the measured fluorescence intensity and the fluorescence intensity of the ionic liquid itself, was approximately 6.4 × 10⁻⁶. 5 .
[0034] Example 2
[0035] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of an ethanol-water solution, and the pH was adjusted to 4. The performance of the solution was then tested using a fluorescence spectrometer. The measured ΔF, the difference between the measured fluorescence intensity and the fluorescence intensity of the ionic liquid itself, was approximately 1.5 × 10⁻⁶. 6 .
[0036] Example 3
[0037] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of ethanol-water solution, and the pH was adjusted to 6. Performance testing was performed using a fluorescence spectrometer. The measured ΔF, the difference between the measured fluorescence intensity and the fluorescence intensity of the ionic liquid itself, was approximately 1.5 × 10⁻⁶. 6 .
[0038] Example 4
[0039] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of ethanol-water solution, and the pH was adjusted to 8. Performance testing was performed using a fluorescence spectrometer. The measured ΔF, the difference between the measured fluorescence intensity and the fluorescence intensity of the ionic liquid itself, was approximately 1.3 × 10⁻⁶. 5 .
[0040] Example 5
[0041] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of an ethanol-water solution, and the pH was adjusted to 9. Performance testing was performed using a fluorescence spectrometer. The measured ΔF, the difference between the measured fluorescence intensity and the fluorescence intensity of the ionic liquid itself, was approximately 7.3 × 10⁻⁶. 4 .
[0042] Example 6
[0043] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of an ethanol-water solution, and the pH was adjusted to 10. The performance of the solution was then tested using a fluorescence spectrometer. The measured ΔF, the difference between the measured fluorescence intensity and the fluorescence intensity of the ionic liquid itself, was approximately 1.5 × 10⁻⁶. 4 .
[0044] Example 7
[0045] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of an ethanol-water solution, and the pH was adjusted to 12. The performance of the solution was then tested using a fluorescence spectrometer. The measured ΔF, the difference between the measured fluorescence intensity and the fluorescence intensity of the ionic liquid itself, was approximately 1.7 × 10⁻⁶. 5 .
[0046] Specific detection examples
[0047] Example 8
[0048] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of an aqueous solution of TC (TC concentration of 200 μmol / L), the pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The measured F / F0, i.e., the ratio of the measured fluorescence intensity to the fluorescence intensity of the ionic liquid itself, was approximately 0.1.
[0049] Example 9
[0050] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of an aqueous solution of MTC (MTC concentration of 200 μmol / L), the pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The measured F / F0, i.e., the ratio of the measured fluorescence intensity to the fluorescence intensity of the ionic liquid itself, was approximately 0.08.
[0051] Example 10
[0052] 200 μL of a 10 mmol / L fluorescent liquid was added to a 1600 μL DOX aqueous solution (DOX concentration was 200 μmol / L), the pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The measured F / F0, i.e., the ratio of the measured fluorescence intensity to the fluorescence intensity of the ionic liquid itself, was approximately 0.1.
[0053] Example 11
[0054] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of CTC (CTC concentration of 200 μmol / L), the pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The measured F / F0, i.e., the ratio of the measured fluorescence intensity to the fluorescence intensity of the ionic liquid itself, was approximately 0.13.
[0055] Example 12
[0056] In 1600 μL of NO3 - (NO3) - 200 μL of a 10 mmol / L fluorescent liquid was added to a 200 μmol / L ionic liquid, the pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The measured F / F0, which is the ratio of the measured fluorescence intensity to the fluorescence intensity of the ionic liquid itself, is approximately 0.8.
[0057] Example 13
[0058] In 1600 μL of Na + in (Na +200 μL of a 10 mmol / L fluorescent liquid was added to a 200 μmol / L ionic liquid, the pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The measured F / F0, which is the ratio of the measured fluorescence intensity to the fluorescence intensity of the ionic liquid itself, was approximately 0.6.
[0059] Example 14
[0060] In 1600 μL of Mn 2+ (Mn) 2+ 200 μL of a 10 mmol / L fluorescent liquid was added to a 200 μmol / L ionic liquid, the pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The measured F / F0, which is the ratio of the measured fluorescence intensity to the fluorescence intensity of the ionic liquid itself, is approximately 0.7.
[0061] Example 15
[0062] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of NOR (NOR concentration was 200 μmol / L), the pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The measured F / F0, which is the ratio of the measured fluorescence intensity to the fluorescence intensity of the ionic liquid itself, was approximately 0.5.
[0063] Example 16
[0064] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of NOR (NOR concentration was 200 μmol / L), the pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The measured F / F0, which is the ratio of the measured fluorescence intensity to the fluorescence intensity of the ionic liquid itself, was approximately 0.5.
[0065] Example 17
[0066] 200 μL of a 10 mmol / L fluorescent liquid was added to 1600 μL of sulfadiazine (sulfadiazine concentration of 200 μmol / L), the pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The measured F / F0, which is the ratio of the measured fluorescence intensity to the fluorescence intensity of the ionic liquid itself, was approximately 0.85.
[0067] Example of physical water sample testing
[0068] Example 18
[0069] A 1600 μL sample of Bodou River water was centrifuged and filtered. TC (concentration of 5 μmol / L) was added, along with 200 μL of fluorescent liquid with a concentration of 10 mmol / L. The pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The TC content was determined to be 5.4 μmol / L, with a recovery rate of 107.1% and a precision of 3.2%.
[0070] Example 19
[0071] A 1600 μL sample of Bodou River water was centrifuged and filtered. CTC (5 μmol / L) was added, along with 200 μL of fluorescent liquid with a concentration of 10 mmol / L. The pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The CTC content was determined to be 4.8 μmol / L, with a recovery rate of 97% and a precision of 3.1%.
[0072] Example 20
[0073] A 1600 μL sample of Bodou River water was centrifuged and filtered. MTC (5 μmol / L) was added, along with 200 μL of 10 mmol / L fluorescent liquid. The pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The MTC content was determined to be 5.8 μmol / L, with a recovery rate of 116.6% and a precision of 1.2%.
[0074] Example 21
[0075] A 1600 μL sample of Bodou River water was centrifuged and filtered. DOX (5 μmol / L) was added, along with 200 μL of 10 mmol / L fluorescent liquid. The pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The DOX content was determined to be 5.1 μmol / L, with a recovery rate of 116.0% and a precision of 2.7%.
[0076] Example 22
[0077] Take 1600 μL of mixed water sample 1, centrifuge and filter it, add TC (TC concentration of 25 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The TC content was found to be 23.7 μmol / L, the recovery rate was 102.6%, and the precision was 3.2%.
[0078] Example 23
[0079] Take 1600 μL of mixed water sample 1, centrifuge and filter it, add CTC (CTC concentration of 25 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The CTC content was determined to be 22.6 μmol / L, the recovery rate was 89.2%, and the precision was 2.0%.
[0080] Example 24
[0081] Take 1600 μL of mixed water sample 1, centrifuge and filter it, add MTC (MTC concentration of 25 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The MTC content was found to be 24.6 μmol / L, the recovery rate was 103.4%, and the precision was 1.3%.
[0082] Example 25
[0083] Take 1600 μL of mixed water sample 1, centrifuge and filter it, add DOX (DOX concentration of 25 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The DOX content was found to be 22.8 μmol / L, the recovery rate was 91.0%, and the precision was 1.5%.
[0084] Example 26
[0085] Take 1600 μL of mixed water sample 2, centrifuge and filter it, add TC (TC concentration of 100 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The TC content was determined to be 100.2 μmol / L, the recovery rate was 100.2%, and the precision was 1.9%.
[0086] Example 27
[0087] Take 1600 μL of mixed water sample 2, centrifuge and filter it, add CTC (CTC concentration of 100 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The CTC content was determined to be 103.1 μmol / L, the recovery rate was 103.1%, and the precision was 0.6%.
[0088] Example 28
[0089] Take 1600 μL of mixed water sample 2, centrifuge and filter it, add MTC (MTC concentration of 100 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The MTC content was found to be 88.9 μmol / L, the recovery rate was 88.9%, and the precision was 1.7%.
[0090] Example 29
[0091] Take 1600 μL of mixed water sample 2, centrifuge and filter it, add DOX (DOX concentration of 100 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The DOX content was found to be 97.0 μmol / L, the recovery rate was 97.0%, and the precision was 0.8%.
[0092] Example 30
[0093] Take 1600 μL of mixed water sample 3, centrifuge and filter it, add TC (TC concentration of 25 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The TC content was found to be 23.7 μmol / L, the recovery rate was 94.7%, and the precision was 1.4%.
[0094] Example 31
[0095] Take 1600 μL of mixed water sample 3, centrifuge and filter it, add CTC (CTC concentration of 25 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The CTC content was found to be 22.6 μmol / L, the recovery rate was 90.0%, and the precision was 1.5%.
[0096] Example 32
[0097] Take 1600 μL of mixed water sample 3, centrifuge and filter it, add MTC (MTC concentration of 25 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The MTC content was found to be 24.6 μmol / L, the recovery rate was 98.5%, and the precision was 0.8%.
[0098] Example 33
[0099] Take 1600 μL of mixed water sample 3, centrifuge and filter it, add DOX (DOX concentration of 25 μmol / L), and add 200 μL of fluorescent liquid with a concentration of 10 mmol / L. Adjust the pH to 4, and use a fluorescence spectrometer to test its performance. The DOX content was found to be 21.2 μmol / L, the recovery rate was 84.9%, and the precision was 1.9%.
[0100] Example 34
[0101] A 1600 μL sample of water from the Beijing-Hangzhou Expressway was centrifuged and filtered. TC (concentration of 5 μmol / L) was added, along with 200 μL of fluorescent liquid with a concentration of 10 mmol / L. The pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The results showed that the TC concentration was 5.51 μmol / L, the recovery rate was 110.3%, and the precision was 1.5%.
[0102] Example 35
[0103] A 1600 μL sample of water from the Beijing-Hangzhou Expressway was centrifuged and filtered. CTC (5 μmol / L) was added, along with 200 μL of fluorescent liquid at a concentration of 10 mmol / L. The pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The results showed that the CTC content was 4.7 μmol / L, the recovery rate was 93.6%, and the precision was 3.3%.
[0104] Example 36
[0105] A 1600 μL sample of water from the Beijing-Hangzhou Expressway was centrifuged and filtered. MTC (5 μmol / L) was added, along with 200 μL of a 10 mmol / L fluorescent liquid. The pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The results showed that the MTC concentration was 4.5 μmol / L, the recovery rate was 90.0%, and the precision was 2.3%.
[0106] Example 37
[0107] A 1600 μL sample of water from the Beijing-Hangzhou Expressway was centrifuged and filtered. DOX (5 μmol / L) was added, along with 200 μL of fluorescent liquid at a concentration of 10 mmol / L. The pH was adjusted to 4, and the performance was tested using a fluorescence spectrometer. The results showed that the DOX content was 4.6 μmol / L, the recovery rate was 91.6%, and the precision was 1.1%.
[0108] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements without departing from the principle of the present invention, and these improvements should also be considered within the scope of protection of the present invention.
Claims
1. A method for the specific detection of tetracycline antibiotics in water based on fluorescent ionic liquids, characterized in that, Includes the following steps: Pre-treatment of water samples; Tetrabutyl(naphthoic acid) phosphorus fluorescent ionic liquid was added to a pretreated water sample containing tetracycline antibiotics, and fluorescence detection was performed immediately; the anion of the fluorescent ionic liquid contained a naphthalene ring structure.
2. The method for specific detection of tetracycline antibiotics in water based on fluorescent ionic liquids according to claim 1, characterized in that, The pretreatment of the water sample includes: centrifuging the water sample for 5 minutes, taking the supernatant, and filtering it through a 0.45-μm membrane filter.
3. The method for specific detection of tetracycline antibiotics in water based on fluorescent ionic liquids according to claim 1, characterized in that, The ratio of the fluorescent ionic liquid to the water being tested is 200 μL: 1600 μL; the concentration of the fluorescent ionic liquid is 10 mmol / L; and the concentration of the tetracycline antibiotic is 1-200 μmol / L.
4. The method for specific detection of tetracycline antibiotics in water based on fluorescent ionic liquids according to claim 1, characterized in that, The pH of the water was between 2 and 12 during the test.
5. The method for specific detection of tetracycline antibiotics in water based on fluorescent ionic liquids according to claim 4, characterized in that, The pH of the water was 4 during the test.
6. The method for specific detection of tetracycline antibiotics in water based on fluorescent ionic liquids according to claim 1, characterized in that, The tetracycline antibiotics include at least one of tetracycline (TC), chlortetracycline (CTC), methacycline (MTC), methoxycycline (MOC), doxycycline (DOX), oxytetracycline (OTC), cationic, anionic, other sulfonamide antibiotics, and other quinolone antibiotics.
7. A method for the specific detection of tetracycline antibiotics in water based on fluorescent ionic liquids as described in claim 1, characterized in that, The preparation method of the fluorescent ionic liquid includes the following steps: Weigh 0.8 g of sodium hydroxide (20 mmol) into a beaker, add 6.7 mL of distilled water and shake well to prepare a 3 mol / L sodium hydroxide solution as a solvent; Weigh 3.344 g (19.42 mmol) of 1-naphthoic acid and add it to the prepared sodium hydroxide solution. The molar ratio of sodium hydroxide to 1-naphthoic acid is 1.03:
1. The system is stirred at 30 °C for 24 h in a magnetic stirrer to obtain a yellow liquid. The generated sodium 1-naphthoate solution was completely added to a three-necked flask. 4.27 mL of a 4.53 mol / L tetrabutylphosphine bromide (TPAH) aqueous solution (19.42 mmol) was measured and added to a 250 mL three-necked flask. Nitrogen was used as a protective gas to purge the air from the flask. The flask was sealed with a glass stopper, and the system was kept at 40 °C overnight with a magnetic stirrer. The supernatant was concentrated, and 20 mL of anhydrous ethanol was added. The mixture was allowed to stand overnight. After filtration, rotary evaporation, and vacuum drying, the target product was obtained as an orange-yellow viscous liquid with a yield of 86.3%.
8. A fluorescent ionic liquid obtained by the preparation method as described in claim 7.
9. The fluorescent ionic liquid according to claim 8, characterized in that, The fluorescent ionic liquid is tetrabutyl(naphthoic acid)phosphorus, whose anion contains a naphthalene ring structure. The structure of the fluorescent ionic liquid is as follows: 。 10. The application of the fluorescent ionic liquid as described in claim 8 in the specific detection of tetracycline antibiotics in water.