CN113522248A - 一种喹诺酮类抗生素分子印迹膜及其制备方法、应用 - Google Patents
一种喹诺酮类抗生素分子印迹膜及其制备方法、应用 Download PDFInfo
- Publication number
- CN113522248A CN113522248A CN202110718473.5A CN202110718473A CN113522248A CN 113522248 A CN113522248 A CN 113522248A CN 202110718473 A CN202110718473 A CN 202110718473A CN 113522248 A CN113522248 A CN 113522248A
- Authority
- CN
- China
- Prior art keywords
- molecularly imprinted
- quinolone antibiotic
- titanium dioxide
- quinolone
- imprinted membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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
Images
Classifications
-
- 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
- B01J20/06—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
-
- 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
-
- 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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种喹诺酮类抗生素分子印迹膜,包括:二氧化钛复合基膜和粘附在二氧化钛复合基膜表面的纳米二氧化钛分子印迹层,其中,所述纳米二氧化钛分子印迹层中的模板分子喹诺酮类抗生素被脱除。本发明还公开了上述喹诺酮类抗生素分子印迹膜的制备方法和其应用。本发明对喹诺酮类抗生素具有良好的选择吸附性能,且可以光催化降解,重复利用。
Description
技术领域
本发明涉及分子印迹技术领域,尤其涉及一种喹诺酮类抗生素分子印迹膜及其制备方法、应用。
背景技术
喹诺酮类抗生素广泛用于人类医疗和动物养殖,在体内代谢通常低于25%,大部分以药物原形随粪尿排出体外。大量喹诺酮类抗生素随着生活污水、养殖污水和制药工业废水等不断进入环境,造成水环境污染,各种水体包括河水、海水、地下水等普遍检出喹诺酮类抗生素。不同水环境介质中喹诺酮类抗生素的浓度虽然比较低,但可能诱导病原菌产生耐药性,对生态***和人类健康产生严重威胁。
二氧化钛作为光催化剂可以降解有机污染物,但是二氧化钛呈颗粒状,不易回收利用;可以将二氧化钛固定在薄膜中,来改善其不易回收的问题,但是薄膜对喹诺酮类抗生素没有选择吸附性,会降低二氧化钛对喹诺酮类抗生素的降解性能。
发明内容
基于背景技术存在的技术问题,本发明提出了一种喹诺酮类抗生素分子印迹膜及其制备方法、应用,本发明对喹诺酮类抗生素具有良好的选择吸附性能,且可以光催化降解,重复利用。
本发明提出了一种喹诺酮类抗生素分子印迹膜,包括:二氧化钛复合基膜和粘附在二氧化钛复合基膜表面的纳米二氧化钛分子印迹层,其中,所述纳米二氧化钛分子印迹层中的模板分子喹诺酮类抗生素被脱除。
分子印迹技术(molecular imprinting technology,MIT)是一种兼备构效预定型、特异识别性和普遍实用性的新型检测技术,通过模板分子与功能单体聚合形成具有特异性识别的多重结合位点,然后脱除模板分子后,所得分子印迹聚合物(molecularlyimprinted polymer,MIP)具有与模板分子大小和形状相匹配的三维空穴,该空穴对模板分子及其类似物具有特异选择性。
优选地,喹诺酮类抗生素为诺氟沙星、环丙沙星中的一种。
本发明还提出了上述喹诺酮类抗生素分子印迹膜的制备方法,包括如下步骤:
S1、将钛酸四丁酯溶液和醋酸纤维素溶液混匀,然后纺丝得到复合纤维膜,然后碳化,煅烧得到二氧化钛复合基膜;
S2、将二氧化钛复合基膜置于氟钛酸铵、硼酸和喹诺酮类抗生素的混合水溶液中,静置,然后脱除模板分子喹诺酮类抗生素,得到喹诺酮类抗生素分子印迹膜。
上述纺丝方式可以为静电纺丝等。
优选地,在S1中,醋酸纤维素和钛酸四丁酯的重量比为1:1.6-1.8。
优选地,在S1中,醋酸纤维素溶液的质量分数为10-15%。
优选地,在S1中,醋酸纤维素溶液的溶剂为N-甲基吡咯烷酮。
优选地,在S1中,钛酸四丁酯溶液的pH=3-4。
可以用乙酸等调节钛酸四丁酯溶液的pH。
优选地,在S1中,钛酸四丁酯溶液的溶剂为乙醇。
优选地,在S1中,钛酸四丁酯溶液的质量分数为40-48%。
优选地,在S1中,于40-60℃搅拌2-3h混匀。
优选地,在S1中,碳化温度为280-320℃,碳化时间为3.5-4h。
优选地,在S1中,在惰性气体氛围中煅烧,煅烧温度为550-600℃,煅烧时间为3.5-4h。
优选地,在S2中,于室温静置5-6h。
优选地,在S2中,混合水溶液中,氟钛酸铵、硼酸、喹诺酮类抗生素的摩尔比为1:3-3.5:0.04-0.05。
优选地,在S2中,混合水溶液中,氟钛酸铵的浓度为0.03-0.04mol/L。
本发明用乙酸水溶液洗脱模板分子喹诺酮类抗生素,也可以光催化降解模板分子喹诺酮类抗生素。
本发明还提出了上述喹诺酮类抗生素分子印迹膜在吸附、降解喹诺酮类抗生素中的应用。
上述水可以为去离子水、纯化水等。
有益效果:
1.本发明选用钛酸四丁酯与醋酸纤维素混匀,并在酸性条件反应生成纳米二氧化钛,然后通过纺丝得到复合纤维膜,在经碳化和煅烧得到二氧化钛复合基膜,二氧化钛牢固的固定在碳纤维上,并通过调节钛酸四丁酯与醋酸纤维素的用量,使得基膜具有较大的比表面积,提高二氧化钛复合基膜的吸附性能;
2.然后在二氧化钛复合基膜生成纳米二氧化钛分子印迹层,分子印迹层中的纳米二氧化钛的表面羟基与复合基膜表面的活性基团结合,紧密粘附在复合基膜表面,且分子印迹层中的纳米二氧化钛的表面羟基与模板分子喹诺酮类抗生素中的氨基、氟元素、羧基等活性基团相互作用,固定模板分子,再去除模板分子得到喹诺酮类抗生素分子印迹膜,配合基膜的吸附性能,本发明对喹诺酮类抗生素具有良好的选择吸附性能;
3.复合基膜和分子印迹层中的纳米二氧化钛相互配合,提高本发明的光降解性能,可以集中降解吸附到的喹诺酮类抗生素,提高其对喹诺酮类抗生素的降解性能;并且本发明可以重复使用。
附图说明
图1为诺氟沙星溶液降解曲线图。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明。
实施例1
一种诺氟沙星分子印迹膜的制备方法,包括如下步骤:
S1、将2g醋酸纤维素加入18ml N-甲基吡咯烷酮中溶解得到醋酸纤维素溶液;将3.2g钛酸四丁酯缓慢加入4ml乙醇(乙酸调节pH=4)中,搅拌20min混匀得到钛酸四丁酯溶液;将钛酸四丁酯溶液滴加到醋酸纤维素溶液中,于40℃搅拌3h混匀,然后将其转移至带有内径0.55mm金属针头的50mL针筒中进行静电纺丝(施加电压20kV,接收距离20cm,纺丝速率2mL/min)得到复合纤维膜,然后将复合纤维膜放在管式炉中,于280℃碳化4h,再于氮气氛围中,于550℃煅烧4h,冷却至室温,依次用乙醇、去离子水洗涤2次,烘干得到二氧化钛复合基膜;
S2、将二氧化钛复合基膜置于氟钛酸铵(浓度为0.03mol/L)、硼酸和诺氟沙星的混合水溶液中,于室温静置6h,然后用去离子水洗涤2次,在高压汞灯(波长250nm)下照射30min,再用体积分数为10%的乙酸水溶液洗涤2次,去离子水洗涤2次,晾干得到诺氟沙星分子印迹膜,其中,混合水溶液中,氟钛酸铵、硼酸、诺氟沙星的摩尔比为1:3:0.04。
实施例2
一种环丙沙星分子印迹膜的制备方法,包括如下步骤:
S1、将2g醋酸纤维素加入18ml N-甲基吡咯烷酮中溶解得到醋酸纤维素溶液;将3.6g钛酸四丁酯缓慢加入4ml乙醇(乙酸调节pH=3)中,搅拌20min混匀得到钛酸四丁酯溶液;将钛酸四丁酯溶液滴加到醋酸纤维素溶液中,于60℃搅拌2h混匀,然后将其转移至带有内径0.55mm金属针头的50mL针筒中进行静电纺丝(施加电压20kV,接收距离20cm,纺丝速率2mL/min)得到复合纤维膜,然后将复合纤维膜放在管式炉中,于320℃碳化3.5h,再于氮气氛围中,于600℃煅烧3.5h,冷却至室温,依次用乙醇、去离子水洗涤2次,烘干得到二氧化钛复合基膜;
S2、将二氧化钛复合基膜置于氟钛酸铵(浓度为0.04mol/L)、硼酸和环丙沙星的混合水溶液中,于室温静置5h,然后用去离子水洗涤2次,在高压汞灯(波长250nm)下照射30min,再用体积分数为10%的乙酸水溶液洗涤2次,去离子水洗涤2次,晾干得到环丙沙星分子印迹膜,其中,混合水溶液中,氟钛酸铵、硼酸、环丙沙星的摩尔比为1:3.5:0.05。
实施例3
一种诺氟沙星分子印迹膜的制备方法,包括如下步骤:
S1、将2g醋酸纤维素加入18ml N-甲基吡咯烷酮中溶解得到醋酸纤维素溶液;将3.4g钛酸四丁酯缓慢加入4ml乙醇(乙酸调节pH=3.5)中,搅拌20min混匀得到钛酸四丁酯溶液;将钛酸四丁酯溶液滴加到醋酸纤维素溶液中,于50℃搅拌2.5h混匀,然后将其转移至带有内径0.55mm金属针头的50mL针筒中进行静电纺丝(施加电压20kV,接收距离20cm,纺丝速率2mL/min)得到复合纤维膜,然后将复合纤维膜放在管式炉中,于300℃碳化3.7h,再于氮气氛围中,于580℃煅烧3.7h,冷却至室温,依次用乙醇、去离子水洗涤2次,烘干得到二氧化钛复合基膜;
S2、将二氧化钛复合基膜置于氟钛酸铵(浓度为0.035mol/L)、硼酸和诺氟沙星的混合水溶液中,于室温静置5.5h,然后用去离子水洗涤2次,在高压汞灯(波长250nm)下照射30min,再用体积分数为10%的乙酸水溶液洗涤2次,去离子水洗涤2次,晾干得到诺氟沙星分子印迹膜,其中,混合水溶液中,氟钛酸铵、硼酸、诺氟沙星的摩尔比为1:3.3:0.045。
对比例1
同实施例3中的S1,得到二氧化钛复合基膜。
对比例2
不添加诺氟沙星,其他同实施例3。
实验1
取实施例3、对比例1-2,分别置于10mL的10mg/L的诺氟沙星溶液(溶剂为体积分数为10%的乙酸水溶液)中,于30℃搅拌1.5h后,测量吸附后溶液中诺氟沙星浓度的变化,计算各膜的吸附量,结果如表1所示。
表1吸附结果
分组 | 对比例1 | 对比例2 | 实施例3 |
吸附量ng | 0.55 | 1.12 | 1.66 |
由表1可以看出,本发明制得的分子印迹膜对诺氟沙星的吸附性能远高于对比例1-2。
实验2
取实施例3、对比例1-2,分别置于10mL的10mg/L的诺氟沙星溶液(溶剂为体积分数为10%的乙酸水溶液)中,分别用高压汞灯(250nm)照射,每隔30min用紫外-可见分光光度计测定吸光度,计算诺氟沙星溶液的浓度,结果如图1所示。图1为诺氟沙星溶液降解曲线图。
由图1可以看出,本发明制得的分子印迹膜对诺氟沙星的降解性能远好于对比例1-2。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种喹诺酮类抗生素分子印迹膜,其特征在于,包括:二氧化钛复合基膜和粘附在二氧化钛复合基膜表面的纳米二氧化钛分子印迹层,其中,所述纳米二氧化钛分子印迹层中的模板分子喹诺酮类抗生素被脱除。
2.根据权利要求1所述喹诺酮类抗生素分子印迹膜,其特征在于,喹诺酮类抗生素为诺氟沙星、环丙沙星中的一种。
3.一种如权利要求1所述喹诺酮类抗生素分子印迹膜的制备方法,其特征在于,包括如下步骤:
S1、将钛酸四丁酯溶液和醋酸纤维素溶液混匀,然后纺丝得到复合纤维膜,然后碳化,煅烧得到二氧化钛复合基膜;
S2、将二氧化钛复合基膜置于氟钛酸铵、硼酸和喹诺酮类抗生素的混合水溶液中,静置,然后脱除模板分子喹诺酮类抗生素,得到喹诺酮类抗生素分子印迹膜。
4.根据权利要求3所述喹诺酮类抗生素分子印迹膜的制备方法,其特征在于,在S1中,醋酸纤维素和钛酸四丁酯的重量比为1:1.6-1.8。
5.根据权利要求3或4所述喹诺酮类抗生素分子印迹膜的制备方法,其特征在于,在S1中,醋酸纤维素溶液的质量分数为10-15%;优选地,在S1中,醋酸纤维素溶液的溶剂为N-甲基吡咯烷酮。
6.根据权利要求3-5任一项所述喹诺酮类抗生素分子印迹膜的制备方法,其特征在于,在S1中,钛酸四丁酯溶液的pH=3-4;优选地,在S1中,钛酸四丁酯溶液的溶剂为乙醇;优选地,在S1中,钛酸四丁酯溶液的质量分数为40-48%。
7.根据权利要求3-6任一项所述喹诺酮类抗生素分子印迹膜的制备方法,其特征在于,在S1中,于40-60℃搅拌2-3h混匀;优选地,在S1中,碳化温度为280-320℃,碳化时间为3.5-4h;优选地,在S1中,在惰性气体氛围中煅烧,煅烧温度为550-600℃,煅烧时间为3.5-4h。
8.根据权利要求3-7任一项所述喹诺酮类抗生素分子印迹膜的制备方法,其特征在于,在S2中,于室温静置5-6h。
9.根据权利要求3-8任一项所述喹诺酮类抗生素分子印迹膜的制备方法,其特征在于,在S2中,混合水溶液中,氟钛酸铵、硼酸、喹诺酮类抗生素的摩尔比为1:3-3.5:0.04-0.05;优选地,在S2中,混合水溶液中,氟钛酸铵的浓度为0.03-0.04mol/L。
10.一种如权利要求1或2所述喹诺酮类抗生素分子印迹膜在吸附、降解喹诺酮类抗生素中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110718473.5A CN113522248A (zh) | 2021-06-28 | 2021-06-28 | 一种喹诺酮类抗生素分子印迹膜及其制备方法、应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110718473.5A CN113522248A (zh) | 2021-06-28 | 2021-06-28 | 一种喹诺酮类抗生素分子印迹膜及其制备方法、应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113522248A true CN113522248A (zh) | 2021-10-22 |
Family
ID=78096964
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110718473.5A Pending CN113522248A (zh) | 2021-06-28 | 2021-06-28 | 一种喹诺酮类抗生素分子印迹膜及其制备方法、应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113522248A (zh) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103898676A (zh) * | 2014-03-18 | 2014-07-02 | 天津工业大学 | 一种醋酸纤维素/二氧化钛复合纳米纤维吸附膜及其制备方法 |
CN104944512A (zh) * | 2015-06-17 | 2015-09-30 | 张易祥 | 一种有效降解水中藻毒素的方法 |
CN105561955A (zh) * | 2016-03-03 | 2016-05-11 | 梅庆波 | 一种疏水性纤维素有机纳米粘土复合重金属离子吸附陶粒的制备方法 |
CN107020100A (zh) * | 2017-03-08 | 2017-08-08 | 长安大学 | 一种硅基光催化型磁性分子印迹材料及其制备方法 |
CN107469653A (zh) * | 2017-08-16 | 2017-12-15 | 江苏大学 | 一种富集和分离诺氟沙星的分子印迹复合膜的合成方法 |
CN107638814A (zh) * | 2017-10-20 | 2018-01-30 | 江苏大学 | 一种go/pvdf分子印迹复合膜的制备方法及其应用 |
CN108816058A (zh) * | 2018-06-27 | 2018-11-16 | 江苏大学 | 一种大黄素分子印迹二氧化钛纳米粒子复合膜及其制备方法与应用 |
CN110801809A (zh) * | 2019-11-09 | 2020-02-18 | 浙江大学 | 高吸附能力多孔可见光催化复合材料的制备方法 |
-
2021
- 2021-06-28 CN CN202110718473.5A patent/CN113522248A/zh active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103898676A (zh) * | 2014-03-18 | 2014-07-02 | 天津工业大学 | 一种醋酸纤维素/二氧化钛复合纳米纤维吸附膜及其制备方法 |
CN104944512A (zh) * | 2015-06-17 | 2015-09-30 | 张易祥 | 一种有效降解水中藻毒素的方法 |
CN105561955A (zh) * | 2016-03-03 | 2016-05-11 | 梅庆波 | 一种疏水性纤维素有机纳米粘土复合重金属离子吸附陶粒的制备方法 |
CN107020100A (zh) * | 2017-03-08 | 2017-08-08 | 长安大学 | 一种硅基光催化型磁性分子印迹材料及其制备方法 |
CN107469653A (zh) * | 2017-08-16 | 2017-12-15 | 江苏大学 | 一种富集和分离诺氟沙星的分子印迹复合膜的合成方法 |
CN107638814A (zh) * | 2017-10-20 | 2018-01-30 | 江苏大学 | 一种go/pvdf分子印迹复合膜的制备方法及其应用 |
CN108816058A (zh) * | 2018-06-27 | 2018-11-16 | 江苏大学 | 一种大黄素分子印迹二氧化钛纳米粒子复合膜及其制备方法与应用 |
CN110801809A (zh) * | 2019-11-09 | 2020-02-18 | 浙江大学 | 高吸附能力多孔可见光催化复合材料的制备方法 |
Non-Patent Citations (3)
Title |
---|
李淞: ""分子印迹材料去除水中诺氟沙星污染物的研究"" * |
王红涛;吴玄;赵慧敏;全燮;: "分子印迹膜修饰TiO_2纳米管及其光催化降解盐酸四环素" * |
赵欣: ""TiO2基复合微纳米纤维的制备及其光催化降解性能研究"" * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Raza et al. | Synthesis of biomass trans-anethole based magnetic hollow polymer particles and their applications as renewable adsorbent | |
Ren et al. | Multi-cycle photocatalytic degradation of bezafibrate by a cast polyvinyl alcohol/titanium dioxide (PVA/TiO2) hybrid film | |
CN113231100B (zh) | 共价有机框架海绵复合材料的制备方法及所得产品和在光催化降解抗生素中的应用 | |
CN113457710A (zh) | PDI/g-C3N4/Bi2WO6复合光催化剂及制备方法和应用 | |
CN103212447B (zh) | 一种稀土金属离子印迹负载型复合光催化剂的制备方法 | |
Zhao et al. | Aldehyde-containing nanofibers electrospun from biomass vanillin-derived polymer and their application as adsorbent | |
CN110559868B (zh) | 一种基于点击化学印迹邻氯西林分子复合膜的制备方法及应用 | |
CN113522248A (zh) | 一种喹诺酮类抗生素分子印迹膜及其制备方法、应用 | |
CN100591615C (zh) | 氨基化的磁性碳管与制备方法及其在生物传感器中的应用 | |
CN103301886B (zh) | 一种导电聚合物印迹金属离子负载型光催化剂的制备方法 | |
CN111892735B (zh) | 一种表面修饰光催化剂的反应分离一体膜的制备方法及其应用 | |
CN113460996B (zh) | 一种检测铁离子的荧光碳点、水凝胶和试纸的制备方法 | |
CN105289726B (zh) | 具有专一定向能力的磁性p3ht/tnt异质结光催化剂及其制备方法 | |
CN113368706B (zh) | 一种基于聚多巴胺基印迹策略的仿生抽滤型双层分子印迹纳米纤维复合膜的制备方法及应用 | |
CN112723479B (zh) | 基于多孔聚合物修饰的金属碳纳米管复合膜分离含染料废水的方法 | |
CN108927225A (zh) | 一种用于染料降解的光催化膜制备方法 | |
CN108636363A (zh) | 谷氨酸修饰的碳纳米管复合材料及其制备方法和应用 | |
CN113368708A (zh) | 一种基于多重纳米复合印迹体系的抽滤型双层分子印迹纳米复合膜的制备方法及应用 | |
BR102017022370A2 (pt) | Titânia suportada em membrana de celulose bacteriana | |
CN111560244B (zh) | 一种pH响应的壳聚糖荧光复合胶束及其制备方法和应用 | |
CN110201647A (zh) | 一种聚-吡咯-2,5-二(多元醇甲烷)吸附剂及制备方法 | |
Chen et al. | Solar interfacial evaporation for efficient treatment of sewage containing volatile organic compounds and toxic heavy metal ions: A sequential process of adsorption, coagulation, and evaporation | |
CN111992253A (zh) | 一种用于催化降解抗生素的有机-金属骨架催化剂及其制备方法 | |
Yan et al. | Permselective and transparent wooden membrane with artemisinin-imprinted nanocages based on a MOFs@ C3N4 self-assembly design | |
CN115254045B (zh) | 一种改性淀粉/氧化石墨烯复合气凝胶及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211022 |