Method for selective removal of fluoroquinolone antibiotics by mips functionalized aqueous film forming foam and applications thereof

Abstract

The application discloses a method for selectively removing fluoroquinolone antibiotics by MIP functionalized water film forming foam and application, and belongs to the technical field of water treatment of antibiotic pollution. The application prepares a molecular imprinting polymer (MIP) capable of selectively removing fluoroquinolone antibiotics, mixes the MIP with a non-ionic surfactant, and obtains a foam suspension after high-speed stirring; the foam suspension is introduced into wastewater to be treated, the foam rises under the action of buoyancy, and trace fluoroquinolone antibiotics are efficiently and selectively captured by using specific imprinting cavities on the surface of the MIP in the process of flotation reaction; and finally, the foam layer on the surface of the water body is removed, so that the fluoroquinolone antibiotics in the wastewater are removed. The application constructs a green flotation system by using a non-ionic surfactant, combines specific imprinting recognition with efficient foam carrying, and realizes selective removal of trace antibiotics in complex aquaculture water and rapid separation and recovery of the adsorption material.

Description

Technical Field

[0001] This invention belongs to the field of antibiotic-contaminated water treatment technology, specifically relating to a method and application of selective removal of fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam. Background Technology

[0002] Fluoroquinolone antibiotics (FQs, such as enrofloxacin and ciprofloxacin) are widely used in aquaculture and livestock farming due to their broad-spectrum efficacy, good absorption, and long half-life. However, animals cannot completely absorb these drugs, and large amounts of antibiotics and their metabolites enter natural water bodies through excrement. These trace residues not only induce antibiotic resistance in bacteria in the environment but also accumulate through the food chain, posing a serious threat to aquatic ecosystems and human health. Therefore, developing efficient and green removal technologies for trace FQs in complex aquaculture water bodies has become an urgent need in the field of water environment management and pollution control.

[0003] Currently, the removal of antibiotics from water bodies mainly relies on biochemical methods, advanced oxidation methods, and traditional physical adsorption methods. However, these methods all have significant limitations: biochemical methods have long treatment cycles, demanding conditions for microbial growth, and high concentrations or specific types of antibiotics can inhibit microbial activity, leading to low efficiency; advanced oxidation methods have high operating costs and energy consumption, and are prone to generating intermediate products with unknown toxicity in complex water bodies, posing a risk of secondary pollution; traditional physical adsorption methods (such as activated carbon and macroporous resins) lack specific recognition capabilities, while aquaculture water bodies are rich in complex organic matter such as proteins, polysaccharides, and humic acids, making conventional adsorbents easily competitively adsorbed or encapsulated, resulting in rapid saturation of adsorption capacity and difficulty in regeneration, making it difficult to meet the requirements for deep removal of trace antibiotics.

[0004] Molecularly imprinted polymers (MIPs) use target molecules as templates. After polymerization and elution, specific recognition holes are formed within the MIP that perfectly match the target molecule in terms of spatial configuration and functional groups. Compared to traditional adsorbents, MIPs have significant advantages such as extremely high selectivity, good physicochemical stability, and reusability, effectively resisting interference from complex matrices in aquaculture water. However, MIPs prepared by traditional bulk polymerization are mostly irregular lumps or fine powders, resulting in slow mass transfer rates in aqueous phases. More importantly, their density is similar to that of water, making it difficult to achieve efficient solid-liquid separation through gravity sedimentation or conventional filtration after direct addition. This leads to extremely low material recovery rates, easily causing material loss and secondary pollution.

[0005] To address the challenge of solid-liquid separation, foam flotation technology offers a promising solution. This technology introduces aqueous film-forming foam (AFFB) as a carrier, leveraging its large specific surface area to enhance gas-liquid-solid three-phase mass transfer. The natural buoyancy of the AFFB rapidly carries pollutant-laden microparticles (MIPs) to the water surface, forming a foam layer, thus achieving rapid and low-energy skimming separation. However, commonly used foaming agents in existing flotation technologies (such as anionic surfactants like sodium dodecyl sulfate) are highly toxic to aquatic organisms and difficult to degrade, failing to meet the ecological safety requirements of aquaculture waters. Furthermore, conventional air flotation methods lack the specific capture capability for trace dissolved antibiotics, and relying solely on the physical collision of bubbles cannot achieve deep removal of target pollutants.

[0006] In summary, there is an urgent need to develop a novel foam flotation system that combines environmentally friendly foaming agents with specific MIPs to solve the problems of low antibiotic removal rate, poor selectivity, and difficulty in recovering adsorbent materials in aquaculture water, so as to achieve green and efficient removal and enrichment of antibiotics. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of the prior art and to provide a method and application for selectively removing fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam.

[0008] The specific technical solution adopted in this invention is as follows:

[0009] In a first aspect, the present invention provides a method for selectively removing fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam, the specific steps of which are as follows:

[0010] S1: Mix the fluoroquinolone imprinted polymer with a nonionic surfactant until homogeneous, and generate aqueous film-forming foam by high-speed stirring to obtain a foam suspension loaded with fluoroquinolone imprinted polymer;

[0011] S2: The foam suspension is introduced into the wastewater containing fluoroquinolone antibiotics. The foam rises under the action of buoyancy and undergoes a flotation reaction. During the flotation reaction, the fluoroquinolone imprinted polymer selectively captures the fluoroquinolone antibiotics in the wastewater.

[0012] S3: After the flotation reaction is completed, the foam layer on the surface of the water is removed to remove fluoroquinolone antibiotics from the wastewater.

[0013] Preferably, the method for preparing the fluoroquinolone-imprinted polymer is as follows:

[0014] S11: Dissolve the template molecule and the corresponding functional monomer in the porogen to obtain a prepolymer solution; dissolve the initiator in a mixed solution of divinylbenzene and ethylene glycol dimethacrylate to obtain a crosslinking agent solution; wherein the template molecule is one or more of enrofloxacin, ciprofloxacin, norfloxacin or ofloxacin, and the functional monomer is 2-(trifluoromethyl)acrylic acid, hydroxyethyl methacrylate, methacrylic acid, acrylamide or 4-vinylpyridine;

[0015] S12: Add the crosslinking agent solution to the prepolymer solution, mix well, and then carry out the polymerization reaction under the protection of an inert gas to obtain polymer microspheres containing template molecules;

[0016] S13: Wash the polymer microspheres with an organic eluent until the template molecules are completely eluted; after vacuum drying, a fluoroquinolone imprinted polymer is obtained.

[0017] Furthermore, in step S11, the template molecule is enrofloxacin, and the functional monomers are 2-(trifluoromethyl)acrylic acid and hydroxyethyl methacrylate; the porogen is acetonitrile, ethanol, or chloroform; the initiator is azobisisobutyronitrile; wherein the molar ratio of enrofloxacin, 2-(trifluoromethyl)acrylic acid, hydroxyethyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate, and azobisisobutyronitrile is 1:(4~10):4:(5~20):(5~20):0.1.

[0018] Furthermore, in step S12, the polymerization reaction temperature is controlled at 55~65℃ and the time is 22~26 hours; in step S13, the polymer microspheres are washed sequentially with a mixed solution of methanol and trifluoroacetic acid, pure methanol and pure acetone.

[0019] Preferably, the high-speed stirring rate in step S1 is controlled at 5500~6500 rpm, and the particle size distribution of the aqueous film foam is 50 nm~50 µm.

[0020] Preferably, the nonionic surfactant is Tween-80, Tween-20, or an alkyl glycoside.

[0021] Preferably, the amount of nonionic surfactant added to the foam suspension in step S1 is 0.1~0.5 wt%, and the amount of fluoroquinolone imprinted polymer added is 0.1~0.6 wt%.

[0022] Preferably, the volume ratio of the foam suspension to the wastewater to be treated in step S2 is controlled at 1:(3~15); the flotation reaction time is 30 seconds to 5 minutes.

[0023] Preferably, the fluoroquinolone antibiotic is one or more of enrofloxacin, ciprofloxacin, norfloxacin, ofloxacin, lomefloxacin, gatifloxacin, or sarafloxacin.

[0024] In a second aspect, the present invention provides the application of the method described in the first aspect in the removal of fluoroquinolone antibiotics from aquaculture water.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] (1) This invention combines molecular imprinting technology with aqueous film-forming foam flotation technology, using foam as a carrier to transform the slow sedimentation in traditional solid-liquid separation into rapid mass transfer at the gas-liquid-solid three-phase micro-interface. The molecularly imprinted polymer loaded with the target antibiotic rapidly floats to the water surface with the bubbles and accumulates into a foam layer. Only simple skimming is needed to separate the pollutants from the water, eliminating the need for high-energy-consuming equipment such as centrifugation and filtration, thus significantly reducing operating costs and equipment investment.

[0027] (2) In this invention, a non-toxic, biodegradable nonionic surfactant is used as a foaming agent. It has excellent foam stabilization performance in high-salt and high-hardness water bodies and is safe and harmless to aquatic organisms. It fundamentally overcomes the defect that traditional anionic surfactants cannot be applied to aquaculture water treatment due to toxicity and residual risks.

[0028] (3) The present invention prepares a molecularly imprinted polymer that can specifically recognize antibiotics in water. It adopts a synergistic design of functional monomers, diluent monomers and dual crosslinking agents. 2-(trifluoromethyl)acrylic acid provides strong hydrogen bonds and hydrophobic interactions, hydroxyethyl methacrylate provides hydrophilic groups to improve the dispersibility of the polymer in the aqueous phase, and divinylbenzene and ethylene glycol dimethacrylate jointly construct a crosslinking network that is both rigid and hydrophilic. Thus, imprinted cavities that are completely matched with the spatial configuration of FQs such as enrofloxacin and have multiple complementary forces are constructed inside the polymer. This enables it to accurately and specifically capture trace amounts of fluoroquinolone antibiotics from complex aquaculture water matrices containing a large amount of protein, humic acid and suspended particles, effectively avoiding the problem that traditional adsorbents are easily encapsulated by impurities and quickly become ineffective.

[0029] (4) The molecularly imprinted polymer prepared in this invention adopts a chemical cross-linking polymerization system with a high degree of cross-linking, exhibiting excellent mechanical strength and chemical stability. The MIP after adsorption saturation can be collected along with the foam, efficiently regenerated using a conventional elution system, and reused repeatedly. After multiple cycles, the recognition capacity shows no significant decrease. The entire process is green and low-carbon, conforming to the development direction of water treatment resource utilization. Attached Figure Description

[0030] Figure 1 This is a flowchart illustrating the preparation of the molecularly imprinted polymer in Example 1;

[0031] Figure 2 This is a graph showing the enrofloxacin removal rate in simulated complex substrate aquaculture water in Example 2;

[0032] Figure 3 This is a graph showing the enrofloxacin removal rate in real freshwater aquaculture water in Example 3;

[0033] Figure 4 This is a graph showing the enrofloxacin removal rate in real seawater aquaculture water in Example 4;

[0034] Figure 5 The image shows the results of adding only Tween-80 to remove enrofloxacin from simulated complex substrate aquaculture water in Comparative Example 1. Detailed Implementation

[0035] The present invention will be further described and illustrated below with reference to the accompanying drawings and specific embodiments. The technical features of each embodiment of the present invention can be combined accordingly, provided that there is no mutual conflict.

[0036] Example 1

[0037] This embodiment provides a method for preparing a molecularly imprinted polymer using enrofloxacin as a template molecule, the process of which is as follows: Figure 1 As shown, the details are as follows:

[0038] (1) Pre-assembly: 362 mg of the template molecule enrofloxacin, 350 µL of the functional monomer 2-(trifluoromethyl)acrylic acid (TFMAA), and 496 µL of hydroxyethyl methacrylate (HEMA) were dissolved in 30 mL of porogen acetonitrile to obtain a prepolymer solution. The amounts of enrofloxacin, 2-(trifluoromethyl)acrylic acid, and hydroxyethyl methacrylate in the prepolymer solution were 1 mmol, 4 mmol, and 4 mmol, respectively.

[0039] 25 mg of the initiator azobisisobutyronitrile (ABDV) was dissolved in a mixed solution of two crosslinking agents to obtain a crosslinking agent solution. The mixed solution contained 960 µL of ethylene glycol dimethacrylate (EDMA, 5 mmol) and 1300 µL of divinylbenzene (DVB) (5 mmol).

[0040] (2) Polymerization reaction: The crosslinking agent solution was added to the prepolymer solution, and the mixture was placed in an ultrasonic bath for 5 min to ensure uniform mixing. Argon gas was then introduced for deoxygenation for 10 min. The solution was then transferred to a borosilicate glass reactor equipped with a stirrer. The temperature was increased from 20°C to 60°C over 30 min, and finally maintained at 60°C for 24 hours to carry out the polymerization reaction. After the polymerization reaction was completed, the polymer microspheres were collected by centrifugation at 10,000 rpm for 10 min.

[0041] (3) Template elution: The obtained polymer microspheres were washed sequentially with a mixed solution of methanol and trifluoroacetic acid (95:5, v / v), pure methanol and pure acetone until enrofloxacin in the eluent could not be detected by high performance liquid chromatography, thus completing the removal of template molecules.

[0042] (4) Post-treatment: The eluted polymer microspheres were washed with a mixed solution of methanol and acetone (50:50, v / v) and then vacuum dried for 24 h to obtain enrofloxacin imprinted polymer microspheres.

[0043] As a control, non-imprinted polymer microspheres (NIPs) were prepared by following the same steps as above but without adding the template molecule enrofloxacin.

[0044] Example 2

[0045] This embodiment provides a method for selectively removing enrofloxacin from simulated complex substrate aquaculture water using MIP-functionalized aqueous film-forming foam. The specific steps are as follows:

[0046] (1) Prepare simulated complex substrate aquaculture water: Add enrofloxacin to 1 L of deionized water to make its initial concentration 10 mg / L, and add 50 mg / L of humic acid.

[0047] (2) Construction of the bubble system in the experimental group: 200 mg of enrofloxacin imprinted polymer microspheres (MIP) prepared in Example 1 were dispersed in 1 L of deionized water and 200 mg of Tween-80 (0.2 wt% of water mass) were added. A stable foam suspension with a particle size distribution of 50 nm to 50 μm was generated by ultra-high speed stirring (6000 rpm).

[0048] (3) Flotation adsorption: The foam suspension prepared in step (2) is introduced into a simulated complex substrate aquaculture water body (the volume ratio of foam to simulated complex substrate aquaculture water body is 1:3). The foam rises under the action of buoyancy, and the enrofloxacin imprinted polymer in it selectively captures enrofloxacin in the water body. The flotation reaction time is 30 seconds.

[0049] (4) Separation and detection: After the flotation reaction is completed, the mixture is allowed to stand for 5 minutes. The enrofloxacin-imprinted polymer microspheres, carrying the adsorbed enrofloxacin, float to the surface with the foam, forming a dense scum layer. The scum is collected after skimming. A sample of the purified water from the bottom is taken, and the concentration of residual enrofloxacin is determined by HPLC.

[0050] The experimental procedure for the control group was similar to that for the experimental group, except that enrofloxacin-imprinted polymer microspheres (MIPs) were replaced with non-imprinted polymer microspheres (NIPs) in the bubble system construction step. The results are as follows: Figure 2 As shown.

[0051] according to Figure 2 As can be seen, in this embodiment, the removal rate of enrofloxacin by MIP in the aquaculture water reached 95.6%, and the effluent was clear with no MIP powder residue. In contrast, the removal rate of enrofloxacin by NIP in the aquaculture water was very low and negligible.

[0052] Example 3

[0053] This embodiment provides a method for selectively removing enrofloxacin from real freshwater aquaculture water using MIP-functionalized aqueous film-forming foam. The specific steps are as follows:

[0054] (1) Treatment of the water body to be treated: In this embodiment, the tailwater of a freshwater tilapia aquaculture pond was used. After pre-filtration through a 0.22 μm filter membrane, the background enrofloxacin content in the water body was found to be about 12 μg / L. Enrofloxacin was spiked to 100 μg / L in 1 L of real water sample to obtain the water body to be treated.

[0055] (2) Construction of the bubble system: 200 mg of enrofloxacin-imprinted polymer microspheres prepared in Example 1 were dispersed in 1 L of deionized water and 200 mg of Tween-80 (0.2 wt% of water mass) were added. A stable foam suspension with a particle size distribution of 50 nm to 50 μm was generated by ultra-high speed stirring (6000 rpm).

[0056] (3) Flotation adsorption: The foam suspension prepared in step (2) is introduced into the water body to be treated (the volume ratio of foam to water body to be treated is 1:3). The foam rises under the action of buoyancy, and the enrofloxacin imprinted polymer in it selectively captures enrofloxacin in the water body. The flotation reaction time is 20 minutes.

[0057] (4) Separation and detection: Water samples were selected at different time points during the flotation process and detected using UPLC-MS / MS. The results are as follows: Figure 3 As shown in the figure, the results indicate that after the flotation reaction, the residual concentration of enrofloxacin in the water decreased to 4.5 μg / L, with an actual removal rate of 95.5%.

[0058] Example 4

[0059] This embodiment provides a method for selectively removing enrofloxacin from real seawater aquaculture water using MIP-functionalized aqueous film-forming foam. The specific steps are as follows:

[0060] (1) Treatment of the water body to be treated: In this embodiment, a water sample from a shrimp farming pond was used. The basic water quality parameters of the sample were measured to be salinity 32‰ (salinity meter method), pH 8.1, and dissolved organic matter (TOC) 5.6 mg / L. The salinity was within the typical seawater range (30‰~35‰), classifying it as a high-salinity water body. The enrofloxacin background content was detected by liquid chromatography-tandem mass spectrometry, and the result was not detected (below 5.0 ng / L). Enrofloxacin standard was added to the water body to achieve a theoretical spiked concentration of 100 μg / L, and the mixture was stirred evenly to obtain the water body to be treated.

[0061] (2) Experimental group setup:

[0062] ① Experimental Group: 200 mg of enrofloxacin-imprinted polymer microspheres prepared in Example 1 were dispersed in 1 L of deionized water, and 200 mg of nonionic surfactant Tween-80 (0.2 wt% of water mass) was added. A stable foam suspension with a particle size distribution of 50 nm to 50 μm was generated by ultra-high-speed stirring (6000 rpm). The foam suspension was introduced into the water to be treated (the volume ratio of foam to water to be treated was 1:3). The foam rose under the action of buoyancy, and the enrofloxacin-imprinted polymer selectively captured enrofloxacin in the water. The flotation reaction time was 20 minutes.

[0063] ② Control group 1: The nonionic surfactant Tween-80 was replaced with the anionic surfactant sodium dodecyl sulfate (SDS), and the rest of the operation was the same as the experimental group.

[0064] ③ Control group 2: The nonionic surfactant Tween-80 was replaced with the cationic surfactant cetyltrimethylammonium bromide (CTAB).

[0065] Take 1 L of the above-mentioned water to be treated, add 200 mg of enrofloxacin imprinted polymer microspheres prepared in Example 1 and 200 mg of sodium dodecyl sulfate (SDS, an anionic surfactant).

[0066] Take 1 L of the above-mentioned water to be treated, add 200 mg of the enrofloxacin imprinted polymer microspheres prepared in Example 1 and 200 mg of the above-mentioned enrofloxacin imprinted polymer microspheres, and perform the remaining operations as in the experimental group.

[0067] (3) Results and Analysis: The final enrofloxacin removal rates in the experimental group, control group 1, and control group 2 are as follows: Figure 4 As shown.

[0068] Because seawater contains a large amount of Ca 2+ Mg 2+ The anionic surfactant SDS (control group 1) reacted instantly with Ca in seawater after being added. 2+ Mg2+ Ionic reactions generate insoluble precipitates, leading to the deactivation of the foaming agent. During the flotation process, almost no foam is generated on the water surface, and the enrofloxacin removal rate is only 8.1%. As a cationic surfactant (control group 2), CTAB undergoes significant salting out in high-salinity seawater, resulting in a sharp decline in its foam stabilizing performance. It is also difficult to form a stable foam layer, and the enrofloxacin removal rate is only 11.4%.

[0069] In the experimental group, the added Tween-80 is a nonionic surfactant; its molecules are uncharged and do not react with Ca in seawater. 2+ Mg 2+ The ionic reaction exhibits excellent foam stabilization performance in high-salinity and high-hardness seawater. During the flotation process, a stable and fine foam layer rapidly forms on the water surface, and the MIPs are efficiently carried to the surface by the foam. After 20 minutes of flotation treatment, the removal rate of enrofloxacin reached as high as 93.2%.

[0070] Comparative Example 1

[0071] This comparative example provides a method for removing enrofloxacin from simulated complex substrate aquaculture water by adding only Tween-80. The specific steps are as follows:

[0072] (1) Prepare simulated complex substrate aquaculture water: Add enrofloxacin to 1 L of deionized water to make its initial concentration 10 mg / L, and add 50 mg / L of humic acid.

[0073] (2) Bubble treatment: Add 200 mg Tween-80 to 1 L of water and generate a foam suspension with a particle size distribution of 50 nm to 50 μm by ultra-high speed stirring (6000 rpm). Pass the foam suspension into the water to be treated, control the air-to-water ratio at 1:3, and perform the flotation reaction for 20 minutes.

[0074] (3) Separation and Detection: After the reaction, only a small amount of clear foam was produced on the water surface, with no obvious flocculent or scum layer. Bottom water samples were taken for testing, and the results were as follows: Figure 5 As shown, the removal rate of enrofloxacin in this comparative example was only 3.2%.

[0075] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the invention. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all technical solutions obtained through equivalent substitution or transformation fall within the protection scope of the present invention.

Claims

1. A method for selectively removing fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam, characterized in that, The specific steps are as follows: S1: Mix the fluoroquinolone imprinted polymer with a nonionic surfactant until homogeneous, and generate aqueous film-forming foam by high-speed stirring to obtain a foam suspension loaded with fluoroquinolone imprinted polymer; S2: The foam suspension is introduced into the wastewater containing fluoroquinolone antibiotics. The foam rises under the action of buoyancy and undergoes a flotation reaction. During the flotation reaction, the fluoroquinolone imprinted polymer selectively captures the fluoroquinolone antibiotics in the wastewater. S3: After the flotation reaction is completed, the foam layer on the surface of the water is removed to remove fluoroquinolone antibiotics from the wastewater.

2. The method for selectively removing fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam according to claim 1, characterized in that, The preparation method of the fluoroquinolone-imprinted polymer is as follows: S11: Dissolve the template molecule and the corresponding functional monomer in the porogen to obtain a prepolymer solution; dissolve the initiator in a mixed solution of divinylbenzene and ethylene glycol dimethacrylate to obtain a crosslinking agent solution; wherein the template molecule is one or more of enrofloxacin, ciprofloxacin, norfloxacin or ofloxacin, and the functional monomer is 2-(trifluoromethyl)acrylic acid, hydroxyethyl methacrylate, methacrylic acid, acrylamide or 4-vinylpyridine; S12: Add the crosslinking agent solution to the prepolymer solution, mix well, and then carry out the polymerization reaction under the protection of an inert gas to obtain polymer microspheres containing template molecules; S13: Wash the polymer microspheres with an organic eluent until the template molecules are completely eluted; after vacuum drying, a fluoroquinolone imprinted polymer is obtained.

3. The method for selectively removing fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam according to claim 2, characterized in that, The template molecule in step S11 is enrofloxacin, and the functional monomers are 2-(trifluoromethyl)acrylic acid and hydroxyethyl methacrylate; the porogen is acetonitrile, ethanol or chloroform; the initiator is azobisisobutyronitrile; wherein the molar ratio of enrofloxacin, 2-(trifluoromethyl)acrylic acid, hydroxyethyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate and azobisisobutyronitrile is 1:(4~10):4:(5~20):(5~20):0.

1.

4. The method for selectively removing fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam according to claim 2, characterized in that, In step S12, the polymerization reaction temperature is controlled at 55~65℃ and the time is 22~26 hours; in step S13, the polymer microspheres are washed sequentially with a mixed solution of methanol and trifluoroacetic acid, pure methanol and pure acetone.

5. The method for selectively removing fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam according to claim 1, characterized in that, The high-speed stirring rate in step S1 is controlled at 5500~6500 rpm, and the particle size distribution of the aqueous film foam is 50 nm~50 µm.

6. The method for selectively removing fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam according to claim 1, characterized in that, The nonionic surfactant is Tween-80, Tween-20, or an alkyl glycoside.

7. The method for selectively removing fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam according to claim 1, characterized in that, In step S1, the amount of nonionic surfactant added to the foam suspension is 0.1~0.5 wt%, and the amount of fluoroquinolone imprinted polymer added is 0.1~0.6 wt%.

8. The method for selectively removing fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam according to claim 1, characterized in that, In step S2, the volume ratio of the foam suspension to the wastewater to be treated is controlled at 1:(3~15); the flotation reaction time is 30 seconds to 5 minutes.

9. The method for selectively removing fluoroquinolone antibiotics using MIP-functionalized aqueous film-forming foam according to claim 1, characterized in that, The fluoroquinolone antibiotics are one or more of enrofloxacin, ciprofloxacin, norfloxacin, ofloxacin, lomefloxacin, gatifloxacin, or sarafloxacin.

10. The use of the method according to any one of claims 1 to 9 in the removal of fluoroquinolone antibiotics from aquaculture water.

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