CN113522248A - Quinolone antibiotic molecularly imprinted membrane and preparation method and application thereof - Google Patents
Quinolone antibiotic molecularly imprinted membrane and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 47
- KYGZCKSPAKDVKC-UHFFFAOYSA-N Oxolinic acid Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC2=C1OCO2 KYGZCKSPAKDVKC-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000003306 quinoline derived antiinfective agent Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 26
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 18
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 18
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 40
- 210000004379 membrane Anatomy 0.000 claims description 35
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 25
- 229920002301 cellulose acetate Polymers 0.000 claims description 22
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 18
- 229960001180 norfloxacin Drugs 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 12
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 6
- 229960003405 ciprofloxacin Drugs 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 210000002469 basement membrane Anatomy 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000005406 washing Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000010041 electrostatic spinning Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000003975 animal breeding Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- MDQRDWAGHRLBPA-UHFFFAOYSA-N fluoroamine Chemical group FN MDQRDWAGHRLBPA-UHFFFAOYSA-N 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a quinolone antibiotic molecularly imprinted membrane, which comprises the following components: the nano titanium dioxide composite substrate comprises a titanium dioxide composite substrate film and a nano titanium dioxide molecular imprinting layer adhered to the surface of the titanium dioxide composite substrate film, wherein a template molecule quinolone antibiotic in the nano titanium dioxide molecular imprinting layer is removed. The invention also discloses a preparation method and application of the quinolone antibiotic molecularly imprinted membrane. The invention has good selective adsorption performance on quinolone antibiotics, and can be degraded in a photocatalytic manner and recycled.
Description
Technical Field
The invention relates to the technical field of molecular imprinting, in particular to a quinolone antibiotic molecular imprinting film and a preparation method and application thereof.
Background
Quinolone antibiotics are widely used in human medicine and animal breeding, are usually metabolized in vivo by less than 25%, and are mostly excreted in vitro in the form of a drug along with feces and urine. A large amount of quinolone antibiotics continuously enter the environment along with domestic sewage, aquaculture sewage, pharmaceutical industry wastewater and the like, so that water environment pollution is caused, and the quinolone antibiotics are generally detected in various water bodies including river water, seawater, underground water and the like. Although the concentration of the quinolone antibiotics in different water environment media is lower, pathogenic bacteria can be induced to generate drug resistance, and serious threats are generated to ecological systems and human health.
Titanium dioxide serving as a photocatalyst can degrade organic pollutants, but the titanium dioxide is granular and is not easy to recycle; the titanium dioxide can be fixed in the film to improve the problem that the titanium dioxide is not easy to recycle, but the film has no selective adsorbability to the quinolone antibiotics, and the degradation performance of the titanium dioxide to the quinolone antibiotics can be reduced.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a quinolone antibiotic molecularly imprinted membrane, and a preparation method and application thereof.
The invention provides a quinolone antibiotic molecularly imprinted membrane, which comprises the following components: the nano titanium dioxide composite substrate comprises a titanium dioxide composite substrate film and a nano titanium dioxide molecular imprinting layer adhered to the surface of the titanium dioxide composite substrate film, wherein a template molecule quinolone antibiotic in the nano titanium dioxide molecular imprinting layer is removed.
Molecular Imprinting Technology (MIT) is a novel detection technology with combined functions of structure-effect pre-shaping, specific recognition and general utility, and after a template molecule and a functional monomer are polymerized to form a multiple binding site with specific recognition and then the template molecule is removed, the obtained Molecularly Imprinted Polymer (MIP) has three-dimensional cavities matched with the size and shape of the template molecule, and the cavities have specific selectivity on the template molecule and the like.
Preferably, the quinolone antibiotic is one of norfloxacin and ciprofloxacin.
The invention also provides a preparation method of the quinolone antibiotic molecularly imprinted membrane, which comprises the following steps:
s1, uniformly mixing a tetrabutyl titanate solution and a cellulose acetate solution, spinning to obtain a composite fiber membrane, carbonizing, and calcining to obtain a titanium dioxide composite base membrane;
s2, placing the titanium dioxide composite basement membrane into a mixed aqueous solution of ammonium fluotitanate, boric acid and quinolone antibiotics, standing, and then removing template molecules of the quinolone antibiotics to obtain the quinolone antibiotic molecularly imprinted membrane.
The spinning method may be electrostatic spinning or the like.
Preferably, in S1, the weight ratio of cellulose acetate to tetrabutyl titanate is 1: 1.6-1.8.
Preferably, in S1, the mass fraction of the cellulose acetate solution is 10 to 15%.
Preferably, in S1, the solvent of the cellulose acetate solution is N-methylpyrrolidone.
Preferably, in S1, the solution of tetrabutyltitanate has a pH of 3 to 4.
The pH of the tetrabutyl titanate solution may be adjusted with acetic acid or the like.
Preferably, in S1, the solvent of the tetrabutyl titanate solution is ethanol.
Preferably, in S1, the mass fraction of the tetrabutyl titanate solution is 40-48%.
Preferably, in S1, the mixture is stirred for 2-3h at 40-60 ℃.
Preferably, in S1, the carbonization temperature is 280-320 ℃, and the carbonization time is 3.5-4 h.
Preferably, in S1, calcining is carried out in an inert gas atmosphere, the calcining temperature is 550-600 ℃, and the calcining time is 3.5-4 h.
Preferably, in S2, the mixture is left standing for 5-6h at room temperature.
Preferably, in S2, the molar ratio of the ammonium fluotitanate, the boric acid and the quinolone antibiotic in the mixed aqueous solution is 1:3-3.5: 0.04-0.05.
Preferably, in S2, the concentration of ammonium fluorotitanate in the mixed aqueous solution is 0.03 to 0.04 mol/L.
The invention uses acetic acid water solution to elute the quinolone antibiotics of the template molecule and can also degrade the quinolone antibiotics of the template molecule by photocatalysis.
The invention also provides application of the quinolone antibiotic molecularly imprinted membrane in adsorbing and degrading quinolone antibiotics.
The water may be deionized water, purified water, etc.
Has the advantages that:
1. the preparation method comprises the steps of uniformly mixing tetrabutyl titanate and cellulose acetate, reacting under an acidic condition to generate nano titanium dioxide, spinning to obtain a composite fiber membrane, carbonizing and calcining to obtain a titanium dioxide composite base membrane, wherein the titanium dioxide is firmly fixed on carbon fibers, and the dosage of tetrabutyl titanate and cellulose acetate is adjusted to ensure that the base membrane has a larger specific surface area and improve the adsorption performance of the titanium dioxide composite base membrane;
2. then generating a nano titanium dioxide molecular imprinting layer on a titanium dioxide composite base film, combining the surface hydroxyl of the nano titanium dioxide in the molecular imprinting layer with the active group on the surface of the composite base film, closely adhering to the surface of the composite base film, and enabling the surface hydroxyl of the nano titanium dioxide in the molecular imprinting layer to interact with the active groups such as amino, fluorine, carboxyl and the like in the quinolone antibiotics of template molecules, fixing the template molecules, and then removing the template molecules to obtain the quinolone antibiotic molecular imprinting film, wherein the quinolone antibiotic molecular imprinting film has good selective adsorption performance by matching with the adsorption performance of the base film;
3. the nano titanium dioxide in the composite base film and the molecular imprinting layer are matched with each other, so that the photodegradability of the invention is improved, adsorbed quinolone antibiotics can be degraded in a centralized manner, and the degradation performance of the quinolone antibiotics is improved; and the present invention can be reused.
Drawings
FIG. 1 is a graph showing the degradation profile of norfloxacin solution.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a norfloxacin molecularly imprinted membrane comprises the following steps:
s1, adding 2g of cellulose acetate into 18ml of N-methyl pyrrolidone to dissolve the cellulose acetate to obtain a cellulose acetate solution; slowly adding 3.2g of tetrabutyl titanate into 4ml of ethanol (pH is adjusted to be 4 by acetic acid), and uniformly mixing for 20min to obtain a tetrabutyl titanate solution; dropwise adding a tetrabutyl titanate solution into a cellulose acetate solution, stirring for 3h at 40 ℃, uniformly mixing, transferring the tetrabutyl titanate solution into a 50mL needle cylinder with a metal needle head with the inner diameter of 0.55mm, performing electrostatic spinning (the applied voltage is 20kV, the receiving distance is 20cm, and the spinning speed is 2mL/min) to obtain a composite fiber membrane, then putting the composite fiber membrane into a tube furnace, carbonizing for 4h at 280 ℃, calcining for 4h at 550 ℃ in a nitrogen atmosphere, cooling to room temperature, washing for 2 times with ethanol and deionized water in sequence, and drying to obtain a titanium dioxide composite base membrane;
s2, placing the titanium dioxide composite base film in a mixed aqueous solution of ammonium fluotitanate (the concentration is 0.03mol/L), boric acid and norfloxacin, standing for 6h at room temperature, washing for 2 times by using deionized water, irradiating for 30min under a high-pressure mercury lamp (the wavelength is 250nm), washing for 2 times by using an acetic acid aqueous solution with the volume fraction of 10%, washing for 2 times by using deionized water, and airing to obtain the norfloxacin molecularly imprinted film, wherein the molar ratio of the ammonium fluotitanate, the boric acid and the norfloxacin in the mixed aqueous solution is 1:3: 0.04.
Example 2
A preparation method of a ciprofloxacin molecularly imprinted membrane comprises the following steps:
s1, adding 2g of cellulose acetate into 18ml of N-methyl pyrrolidone to dissolve the cellulose acetate to obtain a cellulose acetate solution; slowly adding 3.6g of tetrabutyl titanate into 4ml of ethanol (pH is adjusted to be 3 by acetic acid), and uniformly mixing for 20min to obtain a tetrabutyl titanate solution; dropwise adding a tetrabutyl titanate solution into a cellulose acetate solution, stirring for 2h at 60 ℃, uniformly mixing, transferring the tetrabutyl titanate solution into a 50mL needle cylinder with a metal needle head with the inner diameter of 0.55mm, performing electrostatic spinning (the applied voltage is 20kV, the receiving distance is 20cm, and the spinning speed is 2mL/min) to obtain a composite fiber membrane, then putting the composite fiber membrane into a tube furnace, carbonizing at 320 ℃ for 3.5h, calcining at 600 ℃ for 3.5h in a nitrogen atmosphere, cooling to room temperature, washing with ethanol and deionized water for 2 times in sequence, and drying to obtain a titanium dioxide composite base membrane;
s2, placing the titanium dioxide composite basement membrane in a mixed aqueous solution of ammonium fluotitanate (the concentration is 0.04mol/L), boric acid and ciprofloxacin, standing for 5h at room temperature, then washing for 2 times by deionized water, irradiating for 30min under a high-pressure mercury lamp (the wavelength is 250nm), washing for 2 times by using an acetic acid aqueous solution with the volume fraction of 10%, washing for 2 times by using deionized water, and airing to obtain the ciprofloxacin molecularly imprinted membrane, wherein the molar ratio of the ammonium fluotitanate, the boric acid and the ciprofloxacin in the mixed aqueous solution is 1:3.5: 0.05.
Example 3
A preparation method of a norfloxacin molecularly imprinted membrane comprises the following steps:
s1, adding 2g of cellulose acetate into 18ml of N-methyl pyrrolidone to dissolve the cellulose acetate to obtain a cellulose acetate solution; slowly adding 3.4g of tetrabutyl titanate into 4ml of ethanol (pH is adjusted to be 3.5 by acetic acid), and uniformly mixing for 20min to obtain a tetrabutyl titanate solution; dropwise adding a tetrabutyl titanate solution into a cellulose acetate solution, stirring at 50 ℃ for 2.5 hours, uniformly mixing, transferring the tetrabutyl titanate solution into a 50mL needle cylinder with a metal needle head with the inner diameter of 0.55mm, carrying out electrostatic spinning (the applied voltage is 20kV, the receiving distance is 20cm, and the spinning speed is 2mL/min) to obtain a composite fiber membrane, then putting the composite fiber membrane into a tube furnace, carbonizing at 300 ℃ for 3.7 hours, calcining at 580 ℃ in a nitrogen atmosphere for 3.7 hours, cooling to room temperature, washing with ethanol and deionized water for 2 times in sequence, and drying to obtain a titanium dioxide composite base membrane;
s2, placing the titanium dioxide composite base film in a mixed aqueous solution of ammonium fluotitanate (the concentration is 0.035mol/L), boric acid and norfloxacin, standing for 5.5h at room temperature, washing for 2 times by deionized water, irradiating for 30min under a high-pressure mercury lamp (the wavelength is 250nm), washing for 2 times by an acetic acid aqueous solution with the volume fraction of 10%, washing for 2 times by deionized water, and airing to obtain the norfloxacin molecular imprinted film, wherein the molar ratio of the ammonium fluotitanate, the boric acid and the norfloxacin in the mixed aqueous solution is 1:3.3: 0.045.
Comparative example 1
In the same manner as in S1 of example 3, a titanium dioxide composite base film was obtained.
Comparative example 2
The procedure of example 3 was repeated except that norfloxacin was not added.
Experiment 1
The results of taking example 3 and comparative examples 1 to 2, placing each in 10mL of 10mg/L norfloxacin solution (solvent is 10% by volume acetic acid aqueous solution), stirring at 30 ℃ for 1.5h, measuring the change in norfloxacin concentration in the solution after adsorption, and calculating the adsorption amount of each membrane are shown in Table 1.
TABLE 1 adsorption results
| Grouping | Comparative example 1 | Comparative example 2 | Example 3 |
| Adsorption capacity ng | 0.55 | 1.12 | 1.66 |
As can be seen from Table 1, the adsorption performance of the molecularly imprinted membrane prepared by the method is far higher than that of the molecularly imprinted membrane prepared by the comparative examples 1-2.
The norfloxacin solution of example 3 and comparative examples 1 to 2 were placed in 10mL of 10mg/L norfloxacin solution (the solvent was 10% by volume of acetic acid aqueous solution), irradiated with a high-pressure mercury lamp (250nm), and the absorbance was measured every 30min by an ultraviolet-visible spectrophotometer to calculate the concentration of the norfloxacin solution, and the results are shown in fig. 1. FIG. 1 is a graph showing the degradation profile of norfloxacin solution.
As can be seen from FIG. 1, the degradation performance of the molecularly imprinted membrane prepared by the method is far better than that of comparative examples 1-2.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A quinolone antibiotic molecularly imprinted membrane, comprising: the nano titanium dioxide composite substrate comprises a titanium dioxide composite substrate film and a nano titanium dioxide molecular imprinting layer adhered to the surface of the titanium dioxide composite substrate film, wherein a template molecule quinolone antibiotic in the nano titanium dioxide molecular imprinting layer is removed.
2. The quinolone antibiotic molecularly imprinted membrane according to claim 1, wherein the quinolone antibiotic is one of norfloxacin and ciprofloxacin.
3. A method for preparing a quinolone antibiotic molecularly imprinted membrane according to claim 1, comprising the steps of:
s1, uniformly mixing a tetrabutyl titanate solution and a cellulose acetate solution, spinning to obtain a composite fiber membrane, carbonizing, and calcining to obtain a titanium dioxide composite base membrane;
s2, placing the titanium dioxide composite basement membrane into a mixed aqueous solution of ammonium fluotitanate, boric acid and quinolone antibiotics, standing, and then removing template molecules of the quinolone antibiotics to obtain the quinolone antibiotic molecularly imprinted membrane.
4. The method for preparing a quinolone antibiotic molecularly imprinted membrane according to claim 3, wherein the weight ratio of cellulose acetate to tetrabutyl titanate in S1 is 1:1.6 to 1.8.
5. The method for preparing a quinolone antibiotic molecularly imprinted membrane according to claim 3 or 4, wherein in S1, the mass fraction of the cellulose acetate solution is 10 to 15%; preferably, in S1, the solvent of the cellulose acetate solution is N-methylpyrrolidone.
6. A process for preparing a molecularly imprinted membrane of a quinolone antibiotic according to any one of claims 3 to 5, wherein in S1, the pH of the tetrabutyl titanate solution is 3 to 4; preferably, in S1, the solvent of the tetrabutyl titanate solution is ethanol; preferably, in S1, the mass fraction of the tetrabutyl titanate solution is 40-48%.
7. The method for preparing a quinolone antibiotic molecularly imprinted membrane according to any one of claims 3 to 6, wherein the quinolone antibiotic molecularly imprinted membrane is uniformly mixed in S1 at 40-60 ℃ for 2-3 hours; preferably, in S1, the carbonization temperature is 280-320 ℃, and the carbonization time is 3.5-4 h; preferably, in S1, calcining is carried out in an inert gas atmosphere, the calcining temperature is 550-600 ℃, and the calcining time is 3.5-4 h.
8. The method for preparing a quinolone antibiotic molecularly imprinted membrane according to any one of claims 3 to 7, wherein the membrane is allowed to stand at room temperature for 5 to 6 hours in S2.
9. The method for preparing a quinolone antibiotic molecularly imprinted membrane according to any one of claims 3 to 8, wherein in S2, the molar ratio of ammonium fluorotitanate, boric acid, and quinolone antibiotic in the mixed aqueous solution is 1:3 to 3.5:0.04 to 0.05; preferably, in S2, the concentration of ammonium fluorotitanate in the mixed aqueous solution is 0.03 to 0.04 mol/L.
10. The use of the quinolone antibiotic molecularly imprinted membrane of claim 1 or 2 for adsorbing and degrading quinolone antibiotics.
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Application publication date: 20211022 |