CN109364768A - The preparation method of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material - Google Patents
The preparation method of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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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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- 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
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3064—Addition of pore forming agents, e.g. pore inducing or porogenic agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses the preparation methods of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material, belong to new material technology field.First prepare inorganic silicon nanosphere (SiO2) carry out surface it is modified, it is grafted with polyethyleneimine (PEI), prepare organic inorganic hybridization SN-PEI nanoparticle, it with Kynoar (PVDF) film carries out that obtained basement membrane is blended later, finally using Enoxacin as template molecule, acrylamide (AM) is function monomer, 4-vinylpridine is as crosslinking agent, azo-bis-isobutyl cyanide (AIBN) is that initiator carries out trace polymerization reaction, based on molecular imprinting technology, prepare a kind of high performance organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material (SPEMIMs), and for detecting remaining Enoxacin in waste water.Preparation method of the invention has easy to operate, easy to implement, the features such as yield is higher, and reaction condition is mild, is expected to be applied in industrial production.
Description
Technical field
The present invention relates to a kind of preparation sides of high performance organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material
Method and application belong to new material technology field.
Background technique
Membrane separation technique (MST) refers to natural or artificial synthesized macromolecule membrane, with outside energy or chemical potential difference
For motive force, the method that two-component or multi-component solute and solvent are separated, be classified, purified and be enriched with.UF membrane mistake
Journey is through film using selectivity as separating medium, using film to the difference of mixture each component permeance property, is realized to multicomponent
Separation, purifying and the enrichment of mixture progress physics.The mixture of MST different-grain diameter molecule on a molecular scale is by semi-transparent
When film, the technology of Selective Separation is realized, semi-permeable membrane is also known as seperation film or filter membrane, and membranous wall is covered with aperture, by using cross-flow
The method that filter or dead-end filtration mode are separated.Due to the advantages that it is efficient, energy-saving and environmental protection, at medicine, the energy, waste water
The fields such as reason such as are widely used, and cause material science, biochemistry and chemical engineering at fields scientist and the engineering
The great interest of teacher.But the shortcomings that MST is can not to carry out single, efficient Selective Separation to certain substance, can not be synchronized
Realize efficiently separating for molecule-type and type impurity ion.
Molecular imprinting technology (MIT) is to prepare a kind of technology with molecular specific identification function polymer, when template point
Sub (microsphere, target molecule) is polymerize to obtain solid dielectric in polymer monomer solution with crosslinking agent, is then passed through
The template molecule in medium is either physically or chemically eluted away, obtaining " trace " has target molecule space structure and binding site
MIPs.Surface molecule print technology is by establishing molecular recognition site on the surface of host material, to be conducive to template
The removing of molecule and in conjunction with, preferably resolve conventional molecular engram technology it is whole there is also some major defects, it is such as living
Property site embedding it is too deep, the kinetic rate of mass transfer and charge transfer is slow, and the dynamic performance of adsorption-desorption is bad etc..Recently,
Molecularly imprinted composite membrane imitates the excellent characteristics such as precordainment and extensive practicability by feat of specific recognition, structure, in chromatographic isolation, film
Separation, drug controlled release, chemical sensitisation, is concerned in environment measuring at Solid Phase Extraction.
The advantages of based on both the above technology, and in order to improve the selectivity of molecularly imprinted composite membrane, UF membrane skill
Art is combined with molecular imprinting technology, prepares molecularly imprinted composite membrane.Such as Yilin Wu et al. is prepared for a novel life
Sweet wormwood in the bionical molecularly imprinted composite membrane of object, their binding molecule imprinted polymers and membrane separation technique Selective recognition environment
Element.Jinxing Chen et al. establishes MIP-based chemical sensor, has specific recognition capability to lysozyme.These
Method presents the excellent performance of molecular imprinting technology.Therefore, by the membrane separation technique of high separation capacity and highly selective point
Sub- engram technology combines, and prepares molecularly imprinted composite membrane, and the Norfloxacin detected in water environment has feasibility.
Enoxacin, one kind of the fluoroquinolone antibiotics as the third generation have wide spectrum, strong bactericidal effect, with
Obvious crossing drug resistant is had no between other antibacterials, it is still highly sensitive to the enterobacteriaceae of multidrug resistant the features such as, it is just extensive
Be applied to treatment various bacterial infectious diseases in, wherein most of Enoxacins at all can not be by human and animal's institute's generation
It thanks, it is caused to be ultimately discharged into environment.Since Enoxacin cannot be fully absorbed by human body or animal, have greatly with original
Or the form of metabolite is discharged into environment with excrement and urine, these enter the drug ingedient of ring as environment foreign aid's property
Environmental organism and ecology will be had an impact by closing object, and may finally health to the mankind and existence adversely affect.At this
In secondary invention, by thinking conversion process, Nano carbon balls are successfully fixed on film surface, and combine dopamine bionic adhesion technology,
Successfully having prepared has high-dirt-resistance, hydrophily, water flux, and has highly selective and separation energy to Enoxacin molecule
The molecularly imprinted composite membrane material of power.
Summary of the invention
The molecularly imprinted composite membrane is mainly synthesized by three-step reaction.Firstly, first preparing inorganic silicon nanosphere (SiO2) into
Row surface is modified, is grafted with polyethyleneimine (PEI), and organic inorganic hybridization SN-PEI nanoparticle, Zhi Houyu are prepared
Kynoar (PVDF) film carries out that obtained basement membrane is blended, and finally using Enoxacin as template molecule, acrylamide (AM) is
Function monomer, for 4-vinylpridine as crosslinking agent, azo-bis-isobutyl cyanide (AIBN) is that initiator carries out trace polymerization reaction, base
In molecular imprinting technology, a kind of high performance organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material is prepared
(SPNIMs), and for detecting remaining Enoxacin in waste water.This patent provide preparation method have it is easy to operate, be easy to
The features such as implementation, yield is higher, and reaction condition is mild, is expected to be applied in industrial production.In addition, Static Adsorption and selectivity are seeped
Thoroughly the experimental results showed that prepared molecularly imprinted composite membrane has good separating property and higher selection to Norfloxacin
Property.
The technical solution adopted by the invention is as follows:
The preparation method of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material carries out as steps described below:
(1) preparation of organic inorganic hybridization SN-PEI nanoparticle
By ethyl alcohol, the tetraethyl orthosilicate (TEOS) that ammonium hydroxide and deionized water rapidly join after being sufficiently mixed, wherein
Ethyl alcohol, ammonium hydroxide, deionized water and tetraethyl orthosilicate (TEOS) volume ratio be 50:2.04:0.9:2.9.It is stirred at 25 DEG C
Mix 24 hours, finally will be stirred after SiO2Nanosphere solution is centrifuged for several times with ethyl alcohol, and drying is stand-by.Later, by SiO2
Powder is added in ethyl alcohol, and logical nitrogen 1 as a child heated up, and rapidly joins aminopropyl-triethoxy after temperature is raised to 80 DEG C
After silane (APTES), 80 DEG C back flow reaction 6 hours, after carrying out eccentric cleaning using ethyl alcohol and deionized water, by resulting SN-
NH2 drying is stand-by.Wherein SiO2Powder, ethyl alcohol, aminopropyl triethoxysilane (APTES) usage ratio be 0.3:80:400
(mg:mL: μ L).By SN-NH2It is added in the phosphate buffer solution (PBS) of pH=7.4, carries out ultrasound after 30 minutes, be added penta 2
Aldehyde (GA) is stirred at room temperature 6 hours, resulting SN-GA is centrifuged for several times drying afterwards for use using ethyl alcohol, wherein SN-NH2, phosphoric acid it is slow
Rush solution (PBS), the amount ratio of glutaraldehyde (GA) is 0.3:30:0.5 (mg:mL:mL).Finally, SN-GA is put into the poly- second of 50mL
In alkene imines (PEI) solution, room temperature reaction 6 as a child carried out ethyl alcohol centrifugation for several times, obtained SN-PEI nanometers of organic inorganic hybridization
Particle, drying is stand-by, wherein SN-GA, polyethyleneimine (PEI) amount ratio be 0.25:0.5 (mg:mg/mL).
(2) preparation of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane
Firstly, by PVDF powder and polyvinylpyrrolidone (PVP) and prepared different quality (0.25mg,
0.5mg, 1mg) organic inorganic hybridization SN-PEI nano particle be dissolved in N-Methyl pyrrolidone (NMP) solvent, by flask
Sealing, continued mechanical stirs 24 hours in 60 DEG C of water-bath, to form uniform casting solution, wherein PVDF powder, poly- second
Alkene pyrrolidone (PVP), N-Methyl pyrrolidone (NMP) amount ratio be 4:0.5:20 (g:g:mL).Later, it is vacuumized
2 hours, remove the bubble in casting solution.Then on a glass by casting solution, knifing is carried out, the glass of casting solution will be covered with
Plate immerses at once mutually to be converted in deionized water.Completely after solidification, the organic inorganic hybridization blend film of synthesis (S1, S2,
S3 it) is detached from glass plate and stores 24 hours in deionized water, taking-up is dried stand-by.
(3) preparation of Enoxacin molecularly imprinted composite membrane (SPEMIMs)
Firstly, acrylamide (AM) and object Enoxacin are put into flask by 4-vinylpridine, ethyl alcohol is added
As solvent, carries out being protected from light desire polymerization reaction stirring 3h, 2-3 piece organic inorganic hybridization blend film is put into flask, nitrogen is led to
10 minutes, azo-bis-isobutyl cyanide (AIBN) was added later and carries out initiated polymerization for removal air, after continuing logical 10 minutes nitrogen
It is sealed processing, is put into 60 DEG C of water-baths and carries out trace polymerization reaction 24 hours, reaction takes out resulting SPEMIMs later,
It carries out alcohol to wash, wash respectively three times (10 minute/time), be dried at room temperature, wherein 4-vinylpridine, acrylamide
(AM), Enoxacin, ethyl alcohol, azo-bis-isobutyl cyanide (AIBN) amount ratio be 0.042:0.14:0.3:50:50 (g:g:mmol:
ML:mg).Non- trace composite membrane (SPNIMs) item as a comparison is prepared by the same method.Described in above-mentioned technical proposal
Phosphate buffer solution (PBS), it acts as buffer solutions.
Polyvinylpyrrolidone (PVP) as described in the above technical scheme, it acts as pore-foaming agents.
N-Methyl pyrrolidone (NMP) as described in the above technical scheme, it acts as solvents.
Enoxacin as described in the above technical scheme, it acts as provide template ion.
Acrylamide (AM) as described in the above technical scheme, it acts as function monomers.
Azodiisobutyronitrile (AIBN) as described in the above technical scheme, it acts as initiators.
Technological merit of the invention
Poly- two vinylidene fluoride film as described in the above technical scheme, it acts as support membrane materials.Technology of the invention is excellent
Point:
(1) present invention utilizes organic inorganic hybridization SN-PEI nano particle blending technology, Effective Regulation interlamellar spacing, tool
There is high-mechanical property, improve its hydrophily, the features such as effective recognition site is more, greatly reduces non-specific adsorption.
(2) have thermal stability good using the Enoxacin molecularly imprinted composite membrane that the present invention obtains, quickly absorption is dynamic
Mechanical property, hence it is evident that specific recognition performance.
(3) binding molecule engram technology of the present invention and UF membrane principle synthesize Enoxacin molecularly imprinted composite membrane, simultaneously
In conjunction with organic inorganic hybridization SN-PEI nano particle blending technology, have the advantages that the stability of stain resistance and PVDF are good.
Beneficial effect
A kind of preparation of high performance organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material, and blotting membrane is used
It is tested in the competitive Adsorption of Enoxacin and its analogue.The blotting membrane has selectivity high Enoxacin, and separation is imitated
The advantages of fruit is significant, reuses often.In recent years, molecularly imprinted polymer (MIPs) was concerned.Because material avoids
The disadvantage of traditional MIPs, can be with binding template molecule, specific identification hole, by it in conjunction with membrane separation technique, to molecular engram
The development of technology it is of great significance to.The present invention shows molecularly imprinted composite membrane to be had extensively in new material technology field
Wealthy application prospect.
Detailed description of the invention
The technology of the present invention is further described with reference to the accompanying drawings and examples.
Static adsorbance and Lang Gemiaoer equation model curve of Fig. 1: the SPEMIMs and SPENIMs to object, competitor
(embodiment 2)；
Fig. 2: SPEMIMs to the infiltration capacity (embodiment 2) of object, competitor；
Specific embodiment
Absorption property analysis test method of the present invention specifically:
(i) Static Adsorption is tested
The Enoxacin molecular engram film of certain mass is taken to be added in corresponding test solution, water bath with thermostatic control concussion is investigated not
With influence of the initial concentration to composite membrane of adsorbent solution, after absorption after the completion of, unadsorbed Enoxacin molecular concentration UV-
Vis measurement, and adsorption capacity (Qe, mg/g) is calculated according to result:
Wherein C0(mg/L) and CeIt (mg/L) is the concentration for adsorbing front and back Enoxacin respectively, m (g) is adsorbent amount, V
It (mL) is test fluid volume.
(ii) differential permeability is tested
It makes two identical aquariums with ground branch pipe by oneself, blotting membrane or blank film is fixed on two with clip
Among a aquarium, H-shaped osmotic device is formed, guarantees that two ponds do not leak, it is Enoxacin and promise that substrate is added in a pond
Aqueous solvent is added in another pond in the aqueous solution of Flucloxacillin, samples every certain time, measurement through polymer film substrate it is dense
Degree, and infiltration capacity is calculated accordingly.
Below with reference to specific implementation example, the present invention will be further described.
Embodiment 1
(1) preparation of organic inorganic hybridization SN-PEI nanoparticle
By ethyl alcohol, the tetraethyl orthosilicate (TEOS) that ammonium hydroxide and deionized water rapidly join after being sufficiently mixed, wherein
Ethyl alcohol, ammonium hydroxide, deionized water and tetraethyl orthosilicate (TEOS) volume ratio be 50:2.04:0.9:2.9.It is stirred at 25 DEG C
Mix 24 hours, finally will be stirred after SiO2Nanosphere solution is centrifuged for several times with ethyl alcohol, and drying is stand-by.Later, by SiO2
Powder is added in ethyl alcohol, and logical nitrogen 1 as a child heated up, and rapidly joins aminopropyl-triethoxy after temperature is raised to 80 DEG C
After silane (APTES), 80 DEG C back flow reaction 6 hours, after carrying out eccentric cleaning using ethyl alcohol and deionized water, by resulting SN-
NH2Drying is stand-by.Wherein SiO2Powder, ethyl alcohol, aminopropyl triethoxysilane (APTES) usage ratio be 0.3:80:400
(mg:mL: μ L).By SN-NH2It is added in the phosphate buffer solution (PBS) of pH=7.4, carries out ultrasound after 30 minutes, be added penta 2
Aldehyde (GA) is stirred at room temperature 6 hours, resulting SN-GA is centrifuged for several times drying afterwards for use using ethyl alcohol, wherein SN-NH2, phosphoric acid it is slow
Rush solution (PBS), the amount ratio of glutaraldehyde (GA) is 0.3:30:0.5 (mg:mL:mL).Finally, SN-GA is put into the poly- second of 50mL
In alkene imines (PEI) solution, room temperature reaction 6 as a child carried out ethyl alcohol centrifugation for several times, obtained SN-PEI nanometers of organic inorganic hybridization
Particle, drying is stand-by, wherein SN-GA, polyethyleneimine (PEI) amount ratio be 0.25:0.5 (mg:mg/mL).
(2) preparation of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane
Firstly, by the organic inorganic hybridization of PVDF powder and polyvinylpyrrolidone (PVP) and prepared 0.25mg
SN-PEI nano particle is dissolved in N-Methyl pyrrolidone (NMP) solvent, and flask is sealed, and is continued in 60 DEG C of water-bath
Mechanical stirring 24 hours, to form uniform casting solution, wherein PVDF powder, polyvinylpyrrolidone (PVP), N- methylpyrrole
The amount ratio of alkanone (NMP) is 4:0.5:20 (g:g:mL).Later, it carries out vacuumizing 2 hours, removes the bubble in casting solution.
Then on a glass by casting solution, carry out knifing, by the glass plate for being covered with casting solution immerse at once in deionized water into
Row is mutually converted.Completely after solidification, the organic inorganic hybridization blend film (S1, S2, S3) of synthesis be detached from glass plate and be stored in from
24 hours in sub- water, taking-up is dried stand-by.
(3) preparation of Enoxacin molecularly imprinted composite membrane (SPEMIMs)
Firstly, acrylamide (AM) and object Enoxacin are put into flask by 4-vinylpridine, ethyl alcohol is added
As solvent, carries out being protected from light desire polymerization reaction stirring 3h, 2-3 piece organic inorganic hybridization blend film is put into flask, nitrogen is led to
10 minutes, azo-bis-isobutyl cyanide (AIBN) was added later and carries out initiated polymerization for removal air, after continuing logical 10 minutes nitrogen
It is sealed processing, is put into 60 DEG C of water-baths and carries out trace polymerization reaction 12 hours, reaction takes out resulting SPEMIMs later,
It carries out alcohol to wash, wash respectively three times (10 minute/time), be dried at room temperature, wherein 4-vinylpridine, acrylamide
(AM), Enoxacin, ethyl alcohol, azo-bis-isobutyl cyanide (AIBN) amount ratio be 0.042:0.14:0.1:50:50 (g:g:mmol:
ML:mg).Non- trace composite membrane (SPNIMs) item as a comparison is prepared by the same method.
(4) Static Adsorption is tested
Blotting membrane and each 5 parts of non-blotting membrane are weighed respectively, is respectively put into 10 conical flasks, and it is dense that 10mL is then respectively added
Degree is the Enoxacin aqueous solution of 5,10,30,50,70,100mg/L, and 3h is shaken in water bath with thermostatic control under the conditions of 25 DEG C, complete after absorption
Cheng Hou, the concentration of unadsorbed Enoxacin molecule is measured with UV-vis, and calculates adsorption capacity according to result.
The result shows that the highest saturated adsorption capacity of Enoxacin molecular engram film is 45.36mg/g, hence it is evident that be higher than non-print
The 7.32mg/g of mark film, and mono layer adsorption can be proved to be by the fitting of langmuir's adsorption isotherm, this be by
In producing effective imprinted sites in molecular engram polymerization process, the energy when encountering the template molecule that space site matches
Achieve the effect that effectively to adsorb template molecule.
(5) differential permeability is tested
It makes two identical aquariums with ground branch pipe by oneself, blotting membrane is fixed on two aquariums with clip
Centre forms H-shaped osmotic device, guarantees that two ponds do not leak, and it is 50mg/L Yi Nuosha that concentration of substrate is separately added into a pond
The aqueous solution of star and Norfloxacin, is added the aqueous solvent of same volume in another pond, sample time is respectively 5,10,15,30,
45,60,90,120,180min, measurement penetrate the concentration of the substrate of polymer film, and calculate infiltration capacity accordingly.
The results show that in the aqueous solution of Enoxacin and Norfloxacin that initial concentration is 50mg/L, sample time difference
For 5,10,15,30,45,60,90,120,180min, the concentration for measuring Enoxacin in blank sample pond is respectively 6.325,
7.745,7.802,8.658,9.510,10.463,12.782,12.659,13.526mg/L, the aqueous solution of Norfloxacin it is dense
Degree is respectively 16.326,19.548,25.365,30.605,34.303,38.775,42.802,45.245,46.387mg/L.
The result shows that Enoxacin molecular engram film has specific recognition to Enoxacin and postpones the infiltration of Enoxacin molecule
Saturating effect, little to two competitor molecular images, this molecular engram film shows preferably selective to template molecule.
Embodiment 2
(1) preparation of organic inorganic hybridization SN-PEI nanoparticle
By ethyl alcohol, the tetraethyl orthosilicate (TEOS) that ammonium hydroxide and deionized water rapidly join after being sufficiently mixed, wherein
Ethyl alcohol, ammonium hydroxide, deionized water and tetraethyl orthosilicate (TEOS) volume ratio be 50:2.04:0.9:2.9.It is stirred at 25 DEG C
Mix 24 hours, finally will be stirred after SiO2Nanosphere solution is centrifuged for several times with ethyl alcohol, and drying is stand-by.Later, by SiO2
Powder is added in ethyl alcohol, and logical nitrogen 1 as a child heated up, and rapidly joins aminopropyl-triethoxy after temperature is raised to 80 DEG C
After silane (APTES), 80 DEG C back flow reaction 6 hours, after carrying out eccentric cleaning using ethyl alcohol and deionized water, by resulting SN-
NH2 drying is stand-by.Wherein SiO2Powder, ethyl alcohol, aminopropyl triethoxysilane (APTES) usage ratio be 0.3:80:400
(mg:mL: μ L).By SN-NH2It is added in the phosphate buffer solution (PBS) of pH=7.4, carries out ultrasound after 30 minutes, be added penta 2
Aldehyde (GA) is stirred at room temperature 6 hours, resulting SN-GA is centrifuged for several times drying afterwards for use using ethyl alcohol, wherein SN-NH2, phosphoric acid it is slow
Rush solution (PBS), the amount ratio of glutaraldehyde (GA) is 0.3:30:0.5 (mg:mL:mL).Finally, SN-GA is put into the poly- second of 50mL
In alkene imines (PEI) solution, room temperature reaction 6 as a child carried out ethyl alcohol centrifugation for several times, obtained SN-PEI nanometers of organic inorganic hybridization
Particle, drying is stand-by, wherein SN-GA, polyethyleneimine (PEI) amount ratio be 0.25:0.5 (mg:mg/mL).
(2) preparation of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane
Firstly, by the organic inorganic hybridization of PVDF powder and polyvinylpyrrolidone (PVP) and prepared 0.5mg
SN-PEI nano particle is dissolved in N-Methyl pyrrolidone (NMP) solvent, and flask is sealed, and is continued in 60 DEG C of water-bath
Mechanical stirring 24 hours, to form uniform casting solution, wherein PVDF powder, polyvinylpyrrolidone (PVP), N- methylpyrrole
The amount ratio of alkanone (NMP) is 4:0.5:20 (g:g:mL).Later, it carries out vacuumizing 2 hours, removes the bubble in casting solution.
Then on a glass by casting solution, carry out knifing, by the glass plate for being covered with casting solution immerse at once in deionized water into
Row is mutually converted.Completely after solidification, the organic inorganic hybridization blend film (S1, S2, S3) of synthesis be detached from glass plate and be stored in from
24 hours in sub- water, taking-up is dried stand-by.
(3) preparation of Enoxacin molecularly imprinted composite membrane (SPEMIMs)
Firstly, acrylamide (AM) and object Enoxacin are put into flask by 4-vinylpridine, ethyl alcohol is added
As solvent, carries out being protected from light desire polymerization reaction stirring 3h, 2-3 piece organic inorganic hybridization blend film is put into flask, nitrogen is led to
10 minutes, azo-bis-isobutyl cyanide (AIBN) was added later and carries out initiated polymerization for removal air, after continuing logical 10 minutes nitrogen
It is sealed processing, is put into 60 DEG C of water-baths and carries out trace polymerization reaction 24 hours, reaction takes out resulting SPEMIMs later,
It carries out alcohol to wash, wash respectively three times (10 minute/time), be dried at room temperature, wherein 4-vinylpridine, acrylamide
(AM), Enoxacin, ethyl alcohol, azo-bis-isobutyl cyanide (AIBN) amount ratio be 0.042:0.14:0.3:50:50 (g:g:mmol:
ML:mg).Non- trace composite membrane (SPNIMs) item as a comparison is prepared by the same method.
(4) Static Adsorption is tested
Blotting membrane and each 5 parts of non-blotting membrane are weighed respectively, is respectively put into 10 conical flasks, and it is dense that 10mL is then respectively added
Degree is the Enoxacin aqueous solution of 5,10,30,50,70,100mg/L, and 3h is shaken in water bath with thermostatic control under the conditions of 25 DEG C, complete after absorption
Cheng Hou, the concentration of unadsorbed Enoxacin molecule is measured with UV-vis, and calculates adsorption capacity according to result.
As shown in Figure 1, the highest saturated adsorption capacity of Enoxacin molecular engram film is 55.94mg/g, hence it is evident that is higher than non-
The 8.64mg/g of blotting membrane, and can be proved to be adsorption process by the fitting of langmuir's adsorption isotherm is monolayer
Absorption, this is because produce effective imprinted sites in molecular engram polymerization process, when encountering what space site matched
It can achieve the effect that effectively to adsorb template molecule when template molecule, and compared with Example 1, saturated adsorption capacity is mentioned
It rises, this is that the template molecule amount that can be proved in molecular engram polymerization process and the change of trace polymerization time can be mentioned effectively
Rise adsorption effect.
The result shows that the highest saturated adsorption capacity of norfloxacin molecular imprinted film is 55.94mg/g, hence it is evident that be higher than non-print
The 8.64mg/g of mark film.
(5) differential permeability is tested
It makes two identical aquariums with ground branch pipe by oneself, blotting membrane is fixed on two aquariums with clip
Centre forms H-shaped osmotic device, guarantees that two ponds do not leak, and it is 50mg/L Yi Nuosha that concentration of substrate is separately added into a pond
The aqueous solution of star and Norfloxacin, is added the aqueous solvent of same volume in another pond, sample time is respectively 5,10,15,30,
45,60,90,120,180min, measurement penetrate the concentration of the substrate of polymer film, and calculate infiltration capacity accordingly.
The results show that in the aqueous solution of Enoxacin and Norfloxacin that initial concentration is 50mg/L, sample time difference
For 5,10,15,30,45,60,90,120,180min, the concentration for measuring Enoxacin in blank sample pond is respectively 5.825,
6.957,7.024,8.420,9.732,11.403,13.652,13.989,14.523mg/L, the aqueous solution of Norfloxacin it is dense
Degree is respectively 15.526,18.524,23.687,28.579,32.013,36.483,40.872,44.215,46.308mg/L.
As shown in Fig. 2, Enoxacin molecular engram film has specific recognition to Enoxacin and postpones Enoxacin molecule
The effect of infiltration, it is little to two competitor molecular images, this molecular engram film show it is preferably selective to template molecule,
It demonstrates again and changes the amount of trace polymerization time and template molecule and effectively increase selectivity to template molecule, reach
Good separating effect.
Embodiment 3
(1) preparation of organic inorganic hybridization SN-PEI nanoparticle
By ethyl alcohol, the tetraethyl orthosilicate (TEOS) that ammonium hydroxide and deionized water rapidly join after being sufficiently mixed, wherein
Ethyl alcohol, ammonium hydroxide, deionized water and tetraethyl orthosilicate (TEOS) volume ratio be 50:2.04:0.9:2.9.It is stirred at 25 DEG C
Mix 24 hours, finally will be stirred after SiO2Nanosphere solution is centrifuged for several times with ethyl alcohol, and drying is stand-by.Later, by SiO2
Powder is added in ethyl alcohol, and logical nitrogen 1 as a child heated up, and rapidly joins aminopropyl-triethoxy after temperature is raised to 80 DEG C
After silane (APTES), 80 DEG C back flow reaction 6 hours, after carrying out eccentric cleaning using ethyl alcohol and deionized water, by resulting SN-
NH2 drying is stand-by.Wherein SiO2Powder, ethyl alcohol, aminopropyl triethoxysilane (APTES) usage ratio be 0.3:80:400
(mg:mL: μ L).By SN-NH2It is added in the phosphate buffer solution (PBS) of pH=7.4, carries out ultrasound after 30 minutes, be added penta 2
Aldehyde (GA) is stirred at room temperature 6 hours, resulting SN-GA is centrifuged for several times drying afterwards for use using ethyl alcohol, wherein SN-NH2, phosphoric acid it is slow
Rush solution (PBS), the amount ratio of glutaraldehyde (GA) is 0.3:30:0.5 (mg:mL:mL).Finally, SN-GA is put into the poly- second of 50mL
In alkene imines (PEI) solution, room temperature reaction 6 as a child carried out ethyl alcohol centrifugation for several times, obtained SN-PEI nanometers of organic inorganic hybridization
Particle, drying is stand-by, wherein SN-GA, polyethyleneimine (PEI) amount ratio be 0.25:0.5 (mg:mg/mL).
(2) preparation of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane
Firstly, by the organic inorganic hybridization SN- of PVDF powder and polyvinylpyrrolidone (PVP) and prepared 1mg
PEI nano particle is dissolved in N-Methyl pyrrolidone (NMP) solvent, and flask is sealed, and continues machine in 60 DEG C of water-bath
Tool stirs 48 hours, to form uniform casting solution, wherein PVDF powder, polyvinylpyrrolidone (PVP), N- crassitude
The amount ratio of ketone (NMP) is 4:0.5:20 (g:g:mL).Later, it carries out vacuumizing 2 hours, removes the bubble in casting solution.So
Afterwards on a glass by casting solution, knifing is carried out, the glass plate for being covered with casting solution is immersed at once and is carried out in deionized water
Mutually convert.Completely after solidification, the organic inorganic hybridization blend film (S1, S2, S3) of synthesis is detached from glass plate and is stored in deionization
24 hours in water, taking-up is dried stand-by.
(3) preparation of Enoxacin molecularly imprinted composite membrane (SPEMIMs)
Firstly, acrylamide (AM) and object Enoxacin are put into flask by 4-vinylpridine, ethyl alcohol is added
As solvent, carries out being protected from light desire polymerization reaction stirring 3h, 2-3 piece organic inorganic hybridization blend film is put into flask, nitrogen is led to
10 minutes, azo-bis-isobutyl cyanide (AIBN) was added later and carries out initiated polymerization for removal air, after continuing logical 10 minutes nitrogen
It is sealed processing, is put into 60 DEG C of water-baths and carries out trace polymerization reaction 48 hours, reaction takes out resulting SPEMIMs later,
It carries out alcohol to wash, wash respectively three times (10 minute/time), be dried at room temperature, wherein 4-vinylpridine, acrylamide
(AM), Enoxacin, ethyl alcohol, azo-bis-isobutyl cyanide (AIBN) amount ratio be 0.042:0.14:0.5:50:50 (g:g:mmol:
ML:mg).Non- trace composite membrane (SPNIMs) item as a comparison is prepared by the same method.
(4) Static Adsorption is tested
Blotting membrane and each 5 parts of non-blotting membrane are weighed respectively, is respectively put into 10 conical flasks, and it is dense that 10mL is then respectively added
Degree is the Enoxacin aqueous solution of 5,10,30,50,70,100mg/L, and 3h is shaken in water bath with thermostatic control under the conditions of 25 DEG C, complete after absorption
Cheng Hou, the concentration of unadsorbed Enoxacin molecule is measured with UV-vis, and calculates adsorption capacity according to result.
The result shows that the highest saturated adsorption capacity of Enoxacin molecular engram film is 48.66mg/g, hence it is evident that be higher than non-print
The 8.35mg/g of mark film, and mono layer adsorption can be proved to be by the fitting of langmuir's adsorption isotherm, this be by
In producing effective imprinted sites in molecular engram polymerization process, the energy when encountering the template molecule that space site matches
Achieve the effect that effectively to adsorb template molecule, but be declined slightly compared to embodiment 2, this may be because increasing template molecule
After amount and trace polymerization time, some effective sites can be embedded with the time, therefore reduce adsorption effect.
(6) differential permeability is tested
It makes two identical aquariums with ground branch pipe by oneself, blotting membrane is fixed on two aquariums with clip
Centre forms H-shaped osmotic device, guarantees that two ponds do not leak, and it is 50mg/L Yi Nuosha that concentration of substrate is separately added into a pond
The aqueous solution of star and Norfloxacin, is added the aqueous solvent of same volume in another pond, sample time is respectively 5,10,15,30,
45,60,90,120,180min, measurement penetrate the concentration of the substrate of polymer film, and calculate infiltration capacity accordingly.
The results show that in the aqueous solution of Enoxacin and Norfloxacin that initial concentration is 50mg/L, sample time difference
For 5,10,15,30,45,60,90,120,180min, the concentration for measuring Enoxacin in blank sample pond is respectively 7.305,
8.024,8.805,9.648,11.010,12.763,14.757,15.930,16.526mg/L, the aqueous solution of Norfloxacin it is dense
Degree is respectively 14.572,16.018,18.305,25.375,32.983,36.9075,40.804,45.025,46.507mg/L.
As a result shown in, Enoxacin molecular engram film has specific recognition to Enoxacin and postpones the infiltration of Enoxacin molecule
Saturating effect, it is little to two competitor molecular images, template molecule is preferably selected although this molecular engram film is shown
Property, but after increasing the amount of trace polymerization time and template molecule, generated imprinted sites during trace polymerization
Embedding and destruction result in the reduction of separating effect.
Claims (7)
1. the preparation method of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material, it is characterised in that as steps described below
It carries out:
(1) preparation of organic inorganic hybridization SN-PEI nanoparticle
By ethyl alcohol, the tetraethyl orthosilicate (TEOS) that ammonium hydroxide and deionized water rapidly join after being sufficiently mixed, wherein ethyl alcohol,
The volume ratio of ammonium hydroxide, deionized water and tetraethyl orthosilicate (TEOS) is 50:2.04:0.9:2.9；It is small that it is stirred to 24 at 25 DEG C
When, finally will be stirred after SiO2Nanosphere solution is centrifuged for several times with ethyl alcohol, and drying is stand-by；Later, by SiO2Powder adds
Enter into ethyl alcohol, logical nitrogen 1 as a child heated up, and rapidly joined aminopropyl triethoxysilane after temperature is raised to 80 DEG C
(APTES) after, 80 DEG C back flow reaction 6 hours, after carrying out eccentric cleaning using ethyl alcohol and deionized water, by resulting SN-NH2It dries
It is dry stand-by；Wherein SiO2Powder, ethyl alcohol, aminopropyl triethoxysilane (APTES) usage ratio be 0.3:80:400 (mg:
ML: μ L)；By SN-NH2It is added in the phosphate buffer solution (PBS) of pH=7.4, carries out ultrasound after 30 minutes, glutaraldehyde is added
(GA) it is stirred at room temperature 6 hours, resulting SN-GA is centrifuged for several times drying afterwards for use using ethyl alcohol, wherein SN-NH2, phosphoric acid buffer
Solution (PBS), glutaraldehyde (GA) amount ratio be 0.3:30:0.5 (mg:mL:mL)；Finally, SN-GA is put into 50mL polyethylene
In imines (PEI) solution, room temperature reaction 6 as a child carried out ethyl alcohol centrifugation for several times, obtained organic inorganic hybridization SN-PEI nanoparticle
Son, drying is stand-by, wherein SN-GA, polyethyleneimine (PEI) amount ratio be 0.25:0.5 (mg:mg/mL)；
(2) preparation of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane
Firstly, by PVDF powder and polyvinylpyrrolidone (PVP) and prepared different quality (0.25mg, 0.5mg,
Organic inorganic hybridization SN-PEI nano particle 1mg) is dissolved in N-Methyl pyrrolidone (NMP) solvent, and flask is sealed,
Continued mechanical stirs 24 hours in 60 DEG C of water-bath, to form uniform casting solution, wherein PVDF powder, polyvinylpyrrolidine
Ketone (PVP), N-Methyl pyrrolidone (NMP) amount ratio be 4:0.5:20 (g:g:mL)；Later, it carries out vacuumizing 2 hours, go
Except the bubble in casting solution；Then on a glass by casting solution, knifing is carried out, the glass plate for being covered with casting solution is sunk at once
Leaching is mutually converted in deionized water；Completely after solidification, the organic inorganic hybridization blend film (S1, S2, S3) of synthesis is detached from glass
Glass plate simultaneously stores 24 hours in deionized water, and taking-up is dried stand-by；
(3) preparation of Enoxacin molecularly imprinted composite membrane (SPEMIMs)
Firstly, acrylamide (AM) and object Enoxacin are put into flask by 4-vinylpridine, ethyl alcohol conduct is added
Solvent is carried out being protected from light desire polymerization reaction stirring 3h, 2-3 piece organic inorganic hybridization blend film is put into flask, logical nitrogen 10 divides
Azo-bis-isobutyl cyanide (AIBN) is added later and carries out initiated polymerization for clock, removal air, continues to carry out after nitrogen for logical 10 minutes
Encapsulation process is put into 60 DEG C of water-baths and carries out trace polymerization reaction 24 hours, and reaction takes out resulting SPEMIMs later, carries out
Alcohol washes, wash it is each dried at room temperature three times (10 minute/time), wherein 4-vinylpridine, acrylamide (AM), according to
Promise sand star, ethyl alcohol, azo-bis-isobutyl cyanide (AIBN) amount ratio be 0.042:0.14:0.3:50:50 (g:g:mmol:mL:mg).
2. the preparation method of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material according to claim 1,
It is characterized in that the phosphate buffer solution (PBS), it acts as buffer solutions.
3. the preparation method of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material according to claim 1,
It is characterized in that the polyvinylpyrrolidone (PVP), it acts as pore-foaming agents.
4. the preparation method of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material according to claim 1,
It is characterized in that the N-Methyl pyrrolidone (NMP), it acts as solvents.
5. the preparation method of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material according to claim 1,
It is characterized in that the Enoxacin, it acts as provide template ion.
6. the preparation method of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material according to claim 1,
It is characterized in that the acrylamide (AM), it acts as function monomers.
7. the preparation method of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material according to claim 1,
It is characterized in that the azodiisobutyronitrile (AIBN), it acts as initiators.
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