CN107469653A - A kind of synthetic method for the molecularly imprinted composite membrane for being enriched with and separating Norfloxacin - Google Patents
A kind of synthetic method for the molecularly imprinted composite membrane for being enriched with and separating Norfloxacin Download PDFInfo
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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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
- B01D67/0002—Organic membrane manufacture
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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
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0424—Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The invention discloses a kind of synthetic method for the molecularly imprinted composite membrane for being enriched with and separating Norfloxacin, belong to new material technology field.The molecularly imprinted composite membrane is mainly synthesized by three-step reaction.First, synthesis of titanium dioxide nano particle；Secondly, in the substrate of titanium dioxide, using Norfloxacin as template molecule, dopamine is function monomer and crosslinking agent, with reference to dopamine bionic principle, synthesizes norfloxacin molecular imprinted polymer；Finally, using regenerated cellulose film as host material, by the method for vacuum filtration, molecularly imprinted polymer is filtered onto film, and for detecting the Norfloxacin remained in water body.Preparation method provided by the invention has easy to operate, easy to implement, the features such as yield is higher, and reaction condition is gentle, is expected to be applied in industrial production.In addition, Static Adsorption and selectively penetrating are test result indicates that prepared molecularly imprinted composite membrane has good separating property and higher selectivity to Norfloxacin.
Description
Technical field
The present invention relates to a kind of preparation and application of high performance Norfloxacin trace composite membrane, category new material technology neck
Domain.
Background technology
China is maximum in the world antibiotics production and using state, but the abuse of antibiotic pollutes the ring of the mankind
Border, bacterial resistance caused by abuse of antibiotics have turned into the public health problem of serious threat human health.Norfloxacin, it is a kind of
Carbostyril antibiotic, the mankind and livestock treatment and culture fishery are just being widely used in, wherein most of promise fluorine are husky
Star can not be metabolized by human and animal at all, cause it to be ultimately discharged into environment.Because Norfloxacin can not be by human body or animal
Fully absorb, there is a big chunk to be discharged into these in environment with excrement and urine in the form of original or metabolite and enter ring
Drug ingedient environmental organism and ecology will be had an impact as environment foreign aid property compound, and the mankind may finally be good for
Health and existence adversely affect.
In recent years, by by with high-hydrophilic, stability and anti-bacterial and anti-fouling metachromia can metal nanometer composite material（Such as
TiO2, Ag, Au etc.）Polymeric film material surface is grafted to, the combination property of membrane material can be greatly improved.For example, multiple
Close film surface and form dispersed and tight binding TiO2Nano particle is the key factor for obtaining high performance membrane material.
The TiO that film surface is formed2Nano particle can assign the lasting hydrophilicity of membrane material and reduce water penetration resistance, while uniformly
Scattered TiO2Nano particle can also effectively reduce the blocking probability of fenestra.
Membrane separation technique refers to the mixture of different-grain diameter molecule on a molecular scale when passing through pellicle, realizes selection
Property separation technology.Membrane separating process has that technological process is simple, energy consumption is relatively low, separation is larger, have a wide range of application, without two
It is secondary pollution, strong adaptability and be easy to recovery the advantages that.But traditional UF membrane can not carry out single, efficient selection to certain material
Property separation, can not synchronously realize efficiently separating for molecule-type and type impurity ion.
Recently, molecularly imprinted polymer (MIPs) is excellent by feat of specific recognition, structure effect precordainment and extensive practicality etc.
Different characteristic, received much concern in chromatographic isolation, UF membrane, SPE, drug controlled release, chemical sensitisation, environment measuring.Point
Sub- engram technology is to work as template molecule（Microsphere）Multiple action site can be formed when being contacted with polymer monomer, passes through polymerization
Process produces specific recognition site, after template molecule removes, is formed in polymer and template molecule steric configuration phase
The site hole of matching, such hole will have selection evident characteristics to template molecule and the like.But molecular engram
Composite membrane (MICMs) because its can solve the problem that MIPs materials the shortcomings that, for example binding ability, binding kineticses performance be bad, living
Property site embedding it is too deep, can not reclaim and cause secondary pollution etc., gradually attracted the concern of increasing scientific worker.
In order to improve MICMs selectivity, membrane separation technique and molecular imprinting technology (MIT) are combined, prepare molecule print
Mark composite membrane.For example, Yilin Wu et al. are prepared for a novel bionic molecularly imprinted composite membrane, their binding molecules
Norfloxacin in imprinted polymer and membrane separation technique Selective recognition environment.Jinxing Chen et al. establish MIP-
Based chemical sensors, there is specific recognition capability to lysozyme.These methods present the Optimality of molecular imprinting technology
Energy.Therefore, the MIT of the membrane separation technique of high separation capacity and high selectivity is combined, prepares molecularly imprinted composite membrane, detected
Norfloxacin in water environment has feasibility.
The content of the invention
The molecularly imprinted composite membrane is mainly synthesized by three-step reaction.First, synthesis of titanium dioxide nano-particle.By TiN
Powder, water, H2O2And NH3•H2O is equably mixed, and is stirred；The mixed solution for taking a part to obtain again mixes with ethanol to be stirred
Mix, after back flow reaction, centrifugation, cleaned, be dried for standby repeatedly with ethanol.Then, by titanium dioxide (TiO2) nano-particle disperses
In trishydroxymethylaminomethane (Tris-HCl) aqueous solution for being 8.5 to pH, Norfloxacin is added, after stirring a few hours, then is added
Enter dopamine (DA) at room temperature continue stirring reaction after, centrifuge, washed repeatedly with second alcohol and water, remove unreacted reaction
Thing, the molecularly imprinted polymer of gained are dried for standby；Finally, taken out with regenerated cellulose film (RC) for host material by vacuum
The method of filter, molecularly imprinted polymer is filtered onto film, after drying, template point is washed away with the mixed solution of methanol and acetic acid
Son, for detecting the Norfloxacin remained in water body.
The technical solution adopted by the present invention is as follows：
A kind of preparation method for the bionical molecularly imprinted composite membrane material for being enriched with and separating Norfloxacin is carried out as steps described below：
（1）The preparation of titanium dioxide nano-particle
In single-necked flask, TiN powder, water, H are added2O2And NH3•H2O mixed solution, stir 1h；A part is taken to obtain again
Mixed solution and ethanol mix, the h of back flow reaction 12；After reaction, the product of synthesis is centrifuged, washed repeatedly with ethanol
For several times, it is dried in vacuo stand-by.
（2）The preparation of molecular engram nano-complex particle
In single-necked flask, first by titanium dioxide (TiO2) nano-particle is distributed to the trishydroxymethylaminomethanes of pH=8.5
(Tris-HCl) in the aqueous solution, Norfloxacin is added, after stirring a few hours, dopamine is added and continues stirring reaction at room temperature
Afterwards, centrifuge, washed repeatedly with second alcohol and water, remove unreacted reactant, the molecularly imprinted polymer drying of gained is standby
With.
（3）The preparation of molecularly imprinted composite membrane
Molecularly imprinted polymer is scattered in aqueous, regenerated cellulose is dispersed in by the method for vacuum filtration
On film, template molecule methanol and acetic acid（V:V=9:1）Mixed liquor further wash, carry out the analysis of selected area update strategy performance and survey
Examination.
Wherein step（1）Middle TiN powder, water, H2O2And NH3•H2O mol ratio is 8:6:5:4
Wherein step（1）Middle TiN powder, water, H2O2And NH3•H2O mixed solution and the volume ratio of ethanol are 2:5
Wherein step（2）The mol ratio of middle titanium dioxide nano-particle and trishydroxymethylaminomethane (Tris-HCl) is 125:8
Wherein step（2）The concentration of middle trishydroxymethylaminomethane (Tris-HCl) aqueous solution is 10 M
Wherein step（2）The mass ratio of middle titanium dioxide nano-particle and Norfloxacin is 10:1
Wherein step（2）The mass ratio of middle dopamine and Norfloxacin is 5:1.
The preparation method of non-trace composite membrane corresponding to the present invention as above, but is not added with Norfloxacin similar to synthetic method.
Wherein, the Norfloxacin described in above-mentioned technical proposal, it act as template molecule.
Dopamine described in above-mentioned technical proposal, it act as function monomer and crosslinking agent.
Regenerated cellulose film described in above-mentioned technical proposal, it act as membrane material.
The technological merit of the present invention：
（1）The present invention occurs, in the regenerated cellulose composite film material surface of function monomer modification, to avoid due to trace polymerization
Segment template molecule because embed it is too deep can not elute the problem of, the blotting membrane high mechanical strength of acquisition, high temperature resistant, identification point is not
Destructible, greatly reduce non-specific adsorption；
（2）Have that heat endurance is good using the Norfloxacin blotting membrane that obtains of the present invention, quick Adsorption Kinetics, hence it is evident that
Specific recognition performance.
（3）Binding molecule engram technology of the present invention and UF membrane principle, prepared by function monomer and crosslinking agent of dopamine
Trace titanium dioxide ball, filter to regenerated cellulose film surface so as to synthesize Norfloxacin trace composite membrane.
Beneficial effect
The present invention is prepared for a kind of bionical molecularly imprinted composite membrane material for being enriched with and separating Norfloxacin, and blotting membrane is used for
The competitive Adsorption of Norfloxacin and its analogue is tested.The blotting membrane has selectivity height, separating effect to Norfloxacin
Significantly, the advantages of reusing often.In recent years, molecularly imprinted polymer (MIPs) received much concern.Because material avoids biography
System MIPs inferior position, can be combined it with membrane separation technique, to molecular engram skill with binding template molecule, specific identification hole
The development of art, there is highly important meaning.The present invention show molecularly imprinted composite membrane have in new material technology field it is wide
Application prospect.
Brief description of the drawings
Fig. 1：The building-up process schematic diagram of norfloxacin molecular imprinted composite membrane.
Fig. 2：Regenerated cellulose film, titanium dioxide nano-particle, non-trace titanium ball, trace titanium ball, molecularly imprinted composite membrane
With the FFIR of non-trace composite membrane, by figure we can see that trace titanium dioxide nano-particle
Successfully it is dispersed in the surface of regenerated cellulose film.
Fig. 3：The competition of norfloxacin molecular imprinted composite membrane and non-trace composite membrane to the adsorbance of different antibiotic is inhaled
Attached detection.By in figure we can see that norfloxacin molecular imprinted composite membrane to the adsorbance of Norfloxacin maximum, Er Feiyin
Mark composite membrane is little to the adsorbance difference of each antibiotic, illustrates that norfloxacin molecular imprinted composite membrane has spy to Norfloxacin
Opposite sex selection recognition reaction.
Embodiment
The technology of the present invention is further described with reference to the accompanying drawings and examples.
Absorption property analysis test method of the present invention is specially：
（i）Static Adsorption is tested
Take the blotting membrane of certain mass to add in corresponding test solution, water bath with thermostatic control concussion, investigate the initial of different adsorbent solutions
Influence of the concentration to composite membrane, after absorption after the completion of, unadsorbed Norfloxacin molecular concentration is determined with UV-vis, and according to knot
Fruit calculate adsorption capacity (QE, mg/g)：
WhereinC 0(mg/L) andC e(mg/L) respectively be absorption before and after Norfloxacin concentration, m (g) is adsorbent amount,
V (mL) is test fluid volume.
（ii）Differential permeability is tested
Make two identical aquariums with ground branch pipe by oneself, blotting membrane or blank film are fixed on two glass with clip
Among glass pond, H-shaped osmotic device is formed, ensures that two ponds do not have seepage, it is that Norfloxacin and Lome are husky that substrate is added in a pond
The aqueous solution of star, add aqueous solvent in another pond, sampled every certain time, measure through the substrate of polymer film concentration, and
Infiltration capacity is calculated accordingly.
With reference to specific implementation example, the present invention will be further described.
Embodiment 1
Fig. 1：The building-up process schematic diagram of norfloxacin molecular imprinted composite membrane.
（1）The preparation of titanium dioxide nano-particle
In single-necked flask, 0.25 g TiN powders, 60 mL water, 8 mL H are added2O2With 8 mL NH3•H2O mixed solution,
Stirring 1 hour；The mixed solution and the mixing of 100 mL ethanol that 40 mL are obtained, back flow reaction 12 hours are taken again；After reaction,
The product of synthesis is centrifuged, washed repeatedly with ethanol for several times, vacuum drying is stand-by.
（2）The preparation of molecular engram nano-complex particle
In single-necked flask, 0.2 g titanium dioxide nano-particles are first distributed to the trihydroxy methyl amino first of 50 mL pH=8.5
Alkane（Tris-HCl）In the aqueous solution, Norfloxacin is added（0.2 g）, after stirring 1 hour, add dopamine（0.1 g）Room temperature
After continuing stirring reaction down, centrifuge, washed repeatedly with second alcohol and water, remove unreacted reactant, the molecule print of gained
Mark polymer is dried for standby.
Fig. 2：Regenerated cellulose film, titanium dioxide nano-particle, non-trace titanium ball, trace titanium ball, molecularly imprinted composite membrane
With the FFIR of non-trace composite membrane, by figure we can see that trace titanium dioxide nano-particle
Successfully it is dispersed in the surface of regenerated cellulose film.
（3）The preparation of molecularly imprinted composite membrane
5 mg molecularly imprinted polymers are dispersed in the 500 mL aqueous solution, are dispersed in by the method for vacuum filtration
On regenerated cellulose film, template molecule methanol and acetic acid（V:V=9:1）Mixed liquor further wash, carry out differential permeability
Can analysis test.
The preparation method of non-trace composite membrane corresponding to the present invention as above, but is not added with Norfloxacin similar to synthetic method.
（4）Static Adsorption is tested
Blotting membrane and each 6 parts of non-blotting membrane are weighed respectively, is respectively put into 12 conical flasks, and then respectively adding 9 mL concentration is
10th, 20,30,50,80, the 100 mg/L Norfloxacin aqueous solution, 25o3 h are shaken in water bath with thermostatic control under the conditions of C, after absorption
After the completion of, the concentration of unadsorbed Norfloxacin molecule is determined with UV-vis, and adsorption capacity is calculated according to result.
As a result show, the highest saturated adsorption capacity of norfloxacin molecular imprinted film is 23.76 mg/g, hence it is evident that higher than non-
6.75 mg/g of blotting membrane.
（5）Selective absorption is tested
Weigh 5 parts of blotting membrane, be respectively put into 5 conical flasks, then respectively add 9 mL concentration be 10,20,30,50,80,
100 mg/L Norfloxacin and Lomefloxacin mixed solution, 25o3 h are shaken in water bath with thermostatic control under the conditions of C, are completed after absorption
Afterwards, the concentration of unadsorbed Norfloxacin and Lomefloxacin molecule is determined with UV-vis, and adsorption capacity is calculated according to result.
As a result show, norfloxacin molecular imprinted film is in competitive Adsorption to the highest adsorbance of template molecule Norfloxacin
For 21.72 mg/g, the highest saturated adsorption capacity to Lomefloxacin is 5.26 mg/g, selective factor B 4.13.
Fig. 3：The competition of norfloxacin molecular imprinted composite membrane and non-trace composite membrane to the adsorbance of different antibiotic is inhaled
Attached detection.By in figure we can see that norfloxacin molecular imprinted composite membrane to the adsorbance of Norfloxacin maximum, Er Feiyin
Mark composite membrane is little to the adsorbance difference of each antibiotic, illustrates that norfloxacin molecular imprinted composite membrane has spy to Norfloxacin
Opposite sex selection recognition reaction.
（6）Differential permeability is tested
Make two identical aquariums with ground branch pipe by oneself, blotting membrane is fixed in two aquariums with clip
Between, H-shaped osmotic device is formed, ensures that two ponds do not have seepage, it is husky for 100 mg/L promises fluorine that concentration of substrate is separately added into a pond
The aqueous solution of star and Lomefloxacin, adds the aqueous solvent of same volume in another pond, sample time is respectively 5,10,15,
30th, 45,60,90,120,180 min, measure pass through the concentration of the substrate of polymer film, and calculate infiltration capacity accordingly.
As a result show, in the Norfloxacin and the aqueous solution of Lomefloxacin that initial concentration is 100 mg/L, sample time point
Not Wei 5,10,15,30,45,60,90,120,180 min, the concentration for measuring Norfloxacin in blank sample pond is respectively 0.98,
2.32nd, 5.10,8.84,10.93,14.81,16.24,21.68,22.58 mg/L, the concentration difference of the aqueous solution of Lomefloxacin
For 3.26,9.49,18.70,25.30,36.35,48.50,55.98,63.59,75.62 mg/L.
Test result indicates that norfloxacin molecular imprinted film has specific recognition and delay Norfloxacin molecule to Norfloxacin
Infiltration.
Embodiment 2
（1）The preparation of titanium dioxide nano-particle
In single-necked flask, 0. 5g TiN powders, 120 mL water, 16 mL H are added2O2With 16 mL NH3•H2O mixing is molten
Liquid, stir 1 hour；The mixed solution and the mixing of 200 mL ethanol that 80 mL are obtained, back flow reaction 12 hours are taken again；Reaction
Afterwards, the product of synthesis is centrifuged, washed repeatedly with ethanol for several times, vacuum drying is stand-by.
（2）The preparation of molecular engram nano-complex particle
In single-necked flask, 0.4 g titanium dioxide nano-particles are first distributed to the trihydroxy methyl amino first of 100mL pH=8.5
Alkane（Tris-HCl）In the aqueous solution, Norfloxacin is added（0.4 g）, after stirring 1 hour, add dopamine（0.2 g）Room temperature
After continuing stirring reaction down, centrifuge, washed repeatedly with second alcohol and water, remove unreacted reactant, the molecule print of gained
Mark polymer is dried for standby.
（3）The preparation of molecularly imprinted composite membrane
5 mg molecularly imprinted polymers are dispersed in the 250 mL aqueous solution, are dispersed in by the method for vacuum filtration
On regenerated cellulose film, template molecule methanol and acetic acid（V:V=9:1）Mixed liquor further wash, carry out differential permeability
Can analysis test.
The preparation method of non-trace composite membrane corresponding to the present invention as above, but is not added with Norfloxacin similar to synthetic method.
（4）Static Adsorption is tested
Blotting membrane and each 6 parts of non-blotting membrane are weighed respectively, is respectively put into 12 conical flasks, then respectively add 10 mL concentration
For 80,100,200,300,400, the 800 mg/L Norfloxacin aqueous solution, 25o3 h are shaken in water bath with thermostatic control under the conditions of C,
After the completion of after absorption, the concentration of unadsorbed Norfloxacin molecule is determined with UV-vis, and adsorption capacity is calculated according to result.
As a result show, the highest saturated adsorption capacity of norfloxacin molecular imprinted film is 21.31 mg/g, hence it is evident that higher than non-
6.51 mg/g of blotting membrane.
（5）Selective absorption is tested
5 parts of blotting membrane is weighed, is respectively put into 5 conical flasks, it is 10,20,30,50,100 then respectively to add 10 mL concentration
Mg/L Norfloxacin and the aqueous solution of Lomefloxacin, 25oUnder the conditions of C water bath with thermostatic control shake 3 h, after absorption after the completion of,
The concentration of unadsorbed Norfloxacin and Lomefloxacin molecule is determined with UV-vis, and adsorption capacity is calculated according to result.
As a result show, norfloxacin molecular imprinted film adsorbs appearance in competitive Adsorption to the highest of template molecule Norfloxacin
Amount reaches 20.76 mg/g, and the highest saturated adsorption capacity to Artemether is 5.47 mg/g, selective factor B 3.79.
（6）Differential permeability is tested
Make two identical aquariums with ground branch pipe by oneself, blotting membrane is fixed in two aquariums with clip
Between, H-shaped osmotic device is formed, ensures that two ponds do not have seepage, the promise fluorine that concentration of substrate is 100 mg/L is separately added into a pond
Sha Xing and the Lomefloxacin aqueous solution, add isometric water in another pond, sample time is respectively 5,10,15,30,45,60,
90th, 120,180 min, measure pass through the concentration of the substrate of polymer film, and calculate infiltration capacity accordingly.
As a result show, in the Norfloxacin and the aqueous solution of Lomefloxacin that initial concentration is 200 mg/L, sample time point
Not Wei 5,10,15,30,45,60,90,120,180 min, the concentration for measuring Norfloxacin in blank sample pond is respectively 0.76,
1.97th, 3.19,7.97,11.67,13.34,16.19,18.94,21.13 mg/L, the concentration for measuring Lomefloxacin are respectively
2.77、8.63、16.13、22.48、35.87、47.11、56.35、65.18、70.19 mg/l。
Test result indicates that norfloxacin molecular imprinted film has specific recognition and delay Norfloxacin molecule to Norfloxacin
Infiltration.
Claims (7)
- A kind of 1. preparation method for the bionical molecularly imprinted composite membrane material for being enriched with and separating Norfloxacin, it is characterised in that according to Following step is carried out（1）The preparation of titanium dioxide nano-particleIn single-necked flask, TiN powder, water, H are added2O2And NH3•H2O mixed solution, stir 1h；Take what a part obtained again Mixed solution mixes with ethanol, back flow reaction 12h；After reaction, the product of synthesis is centrifuged, number is washed repeatedly with ethanol Secondary, vacuum drying is stand-by；（2）The preparation of molecular engram nano-complex particleIn single-necked flask, first by titanium dioxide (TiO2) nano-particle is distributed to the trishydroxymethylaminomethanes of pH=8.5 (Tris-HCl) in the aqueous solution, Norfloxacin is added, after stirring a few hours, dopamine is added and continues stirring reaction at room temperature Afterwards, centrifuge, washed repeatedly with second alcohol and water, remove unreacted reactant, the molecularly imprinted polymer drying of gained is standby With；（3）The preparation of molecularly imprinted composite membraneMolecularly imprinted polymer is scattered in aqueous, regenerated cellulose is dispersed in by the method for vacuum filtration On film, template molecule methanol and acetic acid（V:V=9:1）Mixed liquor further wash, carry out the analysis of selected area update strategy performance and survey Examination.
- A kind of 2. preparation of bionical molecularly imprinted composite membrane material for being enriched with and separating Norfloxacin according to claim 1 Method, it is characterised in that wherein step（1）Middle TiN powder, water, H2O2And NH3•H2O mol ratio is 8:6:5:4.
- A kind of 3. preparation of bionical molecularly imprinted composite membrane material for being enriched with and separating Norfloxacin according to claim 1 Method, it is characterised in that wherein step（1）Middle TiN powder, water, H2O2And NH3•H2O mixed solution and the volume ratio of ethanol are 2:5。
- A kind of 4. preparation of bionical molecularly imprinted composite membrane material for being enriched with and separating Norfloxacin according to claim 1 Method, it is characterised in that wherein step（2）Middle titanium dioxide nano-particle rubs with trishydroxymethylaminomethane (Tris-HCl's) You are than being 125:8.
- A kind of 5. preparation of bionical molecularly imprinted composite membrane material for being enriched with and separating Norfloxacin according to claim 1 Method, it is characterised in that wherein step（2）The concentration of middle trishydroxymethylaminomethane (Tris-HCl) aqueous solution is 10 M.
- A kind of 6. preparation of bionical molecularly imprinted composite membrane material for being enriched with and separating Norfloxacin according to claim 1 Method, it is characterised in that wherein step（2）The mass ratio of middle titanium dioxide nano-particle and Norfloxacin is 10:1.
- A kind of 7. preparation of bionical molecularly imprinted composite membrane material for being enriched with and separating Norfloxacin according to claim 1 Method, it is characterised in that wherein step（2）The mass ratio of middle dopamine and Norfloxacin is 5:1.
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