CN104371131B - A kind of preparation method for the molecular blotting polymer microsphere for having a hydrophilic macromolecule brush - Google Patents
A kind of preparation method for the molecular blotting polymer microsphere for having a hydrophilic macromolecule brush Download PDFInfo
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Abstract
The new method that surface has the molecular blotting polymer microsphere of hydrophilic macromolecule brush is prepared the present invention relates to a kind of.There is the molecular blotting polymer microsphere of hydrophilic macromolecule brush to be to be carried out by the molecular blotting polymer microsphere of surface double bond containing C=C with large hydrophilic molecular chain-transferring agent under general radical initiator existence condition made from chemical coupling reaction on the surface.The present invention has the advantages that synthetic method is simple, applied widely, product structure is clear and definite.The molecular blotting polymer microsphere that gained surface has hydrophilic macromolecule brush has broad application prospects in various fields such as clinical medicine immunoassay, food security, environmental monitoring, biotechnologys.
Description
Art
The new method that surface has the molecular blotting polymer microsphere of hydrophilic macromolecule brush is prepared the present invention relates to a kind of,
Specifically it is exactly to be related to a kind of new surface grafting method, surface can be obtained by this method has hydrophilic macromolecule
The molecular blotting polymer microsphere of brush.
Background technology
Molecular imprinting technology is a kind of new side for the simple and effective for preparing the polymeric acceptor with specific recognition site
Method, polymer therefrom is referred to as molecularly imprinted polymer (Molecularly imprinted polymers, MIPs).
MIPs not only has the advantages that excellent mechanical resistance energy, chemicals-resistant and heat resistance and easy preparation and cost are low, and
Also there is the high-affinity that can be compared favourably with natural biological acceptor and selectivity, thus SPE, chromatographic isolation, immune point
The various fields such as analysis, sensor, imitative enzymatic, organic synthesis, drug delivery and bio-pharmaceutical show huge application prospect,
Focus (Zhang, H. as current molecular recognition area research；Ye, L.；Mosbach, K.J. Mol.Recognit.2006,
19：248-259).
Although molecular engram research has achieved huge progress, in some application fields (such as solid phase extractions) MIPs even
The commercialization practical stage is entered, but the MIPs that people obtain at present generally could be to organic only in organic solution system
Small molecule shows excellent molecular recognition performance, and really suitable for water solution system using organic molecule as template
MIPs is then very limited.This greatly hinders practical applications of the MIPs in the field such as bionical immunoassay and sensor.
Recently, we have developed a series of preparations has hydrophilic macromolecule brush suitable for the surface of water solution system
The new method of MIP microballoons." two-step method " and " one-step method " approach can be divided into by being summed up." two-step method " approach is by sharp first
Preparing surface with controllable/" activity " free radical precipitation polymerization technology, there is controllable free-radical polymerisation to trigger or chain tra nsfer group
MIP microballoons, then again using it as immobilized initiator or chain-transferring agent, the surface controllable free-radical for carrying out hydrophilic monomer gathers
Close, obtaining surface has MIP microballoons (Pan, the G. of hydrophilic macromolecule brush；Zhang, Y.；Guo, X.；Li, C.；Zhang,
H.Biosens.Bioelectron.2010,26,976-982；Pan, G.；Ma, Y.；Zhang, Y.；Guo, X.；Li, C.；
Zhang, H.Soft Matter2011,7,8428-8439)." one-step method " approach be by large hydrophilic molecular chain-transferring agent (or
Macro RAFT agent) it is incorporated into reversible addition and fragmentation chain transfer (RAFT) precipitation polymerization system, one-step method is prepared suitable for pure
The surface of water solution system has MIP particles (Pan, the G. of hydrophilic macromolecule brush；Zhang, Y.；Ma, Y.；Li, C.；
Zhang, H.Angew.Chem.Int.Ed.2011,50,11731-11734；Ma, Y.；Pan, G.；Zhang, Y.；Guo, X.；
Zhang, H.Angew.Chem.Int.Ed.2013,53,1511-1514).Though above two preparation method, which can be prepared, is suitable to water
The surface of solution system has the MIP microballoons of hydrophilic macromolecule brush, but there is also respective shortcoming." one-step method " is due to must
Hydrophilic Macromolecular chain transfer agent must be added directly into molecular imprinting polymer system, this can be to function monomer and template point
Self assembly between son has a negative impact.In addition one-step method complex polymerization systems, cause the hydrophily of gained MIP microsphere surfaces high
The density of molecular brush can not be obtained, therefore limit the structural characterization of product；And " two-step method " approach prepare surface have it is hydrophilic
Property polymer brush MIP microballoons when, the molecular weight of the hydrophilic macromolecule brush that its surface is grafted is influenceed very big by reaction condition,
It is difficult the MIP microballoons for obtaining the hydrophilic macromolecule brush with identical molecular weight during duplication of production, so that product can be largely effected on
The stability of performance.In addition, the molecular weight that the method also has the hydrophilic macromolecule brush on gained MIP microballoons can not be determined directly
Difficulty.
The content of the invention
In terms of overcoming the shortcomings of that above method preparation surface has the MIP microballoons of hydrophilic macromolecule brush, the present invention
There is provided a kind of new preparation method, it is intended to which more prepare surface has the parent for determining molecular weight and grafting density simple and effective
The MIP microballoons of aqueous high molecular brush.The present invention has the advantages that synthetic method is simple, applied widely, product structure is clear and definite.
Technical scheme：
The present invention develops a kind of MIP microballoons by large hydrophilic molecular chain-transferring agent and surface with C=C double bonds
Coupling reaction prepares the easy-to-use method that surface has the MIP microballoons of hydrophilic macromolecule brush, and technical concept is by parent
Chain transfer reaction generation hydrophily occurs for the free radical that aqueous macromolecular chain-transferring agent is produced with general radical initiator first
Macromolecular radical, then the macromolecular radical again with MIP microballoons C=C double bonds react, obtaining surface has hydrophily
The MIP microballoons of polymer brush.
Preparing described surface has the concrete technical scheme of the MIP microballoons of hydrophilic macromolecule brush as follows：
1) the MIP microballoons of surface double bond containing C=C and large hydrophilic molecular chain-transferring agent are pressed into MIP microsphere surfaces C=C double bonds
Fed intake with the mol ratio 1: 1~100 of large hydrophilic molecular chain-transferring agent.
2) general radical initiator and large hydrophilic molecular chain-transferring agent 1: 0.15~30 are fed intake in molar ratio.
3) solvent is fed intake in the MIP microballoons ratio of itself and surface double bond containing C=C for 0.04~2 liter/gram.
4) said components are mixed, sealed after the oxygen in removing system.
5) reaction system of good seal is reacted 1~500 hour at a temperature of 25~200 DEG C, obtain surface have it is hydrophilic
The MIP microballoons of property polymer brush.
The MIP microballoons of surface double bond containing C=C are to be directly obtained by various precipitation polymerization methods or repaiied by MIP microsphere surfaces
Decorations introduce what C=C double bonds were obtained, and the content of its surface C=C double bonds is 0.005~0.50 mM/gram.
The large hydrophilic molecular chain-transferring agent is：Hydrophilic polymer with double thioesters or trithio ester terminal, it is described
Hydrophilic polymer is preferably selected from：Polyalcohols, poly- (lactams), polyurethane, poly- (methyl) acrylic acid, polyacrylamide, polyethylene
Alcohol, polyvinylether, polyester, polyvinylamine, polyethyleneimine, polyalkylene oxide, poly- (carboxylic acid), polyamide, polyanhydride, polyphosphazene, fibre
Tie up element, heparin, glucan, polypeptide, fibrin and elastin laminin, polysaccharide, hyaluronic acid, alginates, gelatin and chitin, in vain
Albumen, oligopeptides, short-chain peptide and oligonucleotides and the copolymer obtained by the monomer for obtaining above-mentioned polymer, more preferably poly- second two
Alcohol, poly-N-isopropyl acrylamide, polymethylacrylic acid 2- hydroxy methacrylates, poly- (methyl) acrylamide, poly- N, N '-dimethyl propylene
Acrylamide, polymethylacrylic acid dimethylamino ethyl ester, it is poly- ([2- (methacryloxy) ethyl ］ dimethyl-(3- sulfopropyls)
Ammonium hydroxide), poly- (3-2-N- methylacryoyloxyethyls-N, N- dimethyl propyl sulfonic acid amine), poly- (2- methacryloxypropyl second
Base phosphocholine), (oxygen (11- (3- sulfonyls oxypropyl trimethyl-glycidyl) hendecane base ester sulphomethyl) ethene-oxygen
Base (dodecyl sulphomethyl) ethene) copolymer, poly- (acrylamido -2- methyl isophthalic acids-propane sulfonic acid), poly- (metering system
Acyl ethyl sulfobetaines), poly- (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride), poly- (3- methacrylic acid sulphur propyl ester potassium
Salt), poly- (4- [dimethyl (2 '-methacryloxyethyl) ammonium] butyrate), poly- (methacrylic acid 3- sulfonic acid propyl ester potassium
Salt), poly- (methyl methacrylate sulfobetaines), poly- (Methacrylamide sulfobetaines), poly- (styrene sulfonate),
Poly- (styrene sulfonic acid), polyacrylic acid, polymethylacrylic acid, polymethyl propylhomoserin sodium, methoxyl group three (ethylene glycol) methyl-prop
Olefin(e) acid ester-methacrylic acid copolymer, PEG, PEG methyl ether methacrylate, polyalkylene oxide, polycyclic
Oxidative ethane, poly- (low PEG methyl ether methacrylate), poly- (methacrylic acid oxyethylene glycol ester), poly- (N- methyl
Glycine), PLGA, PLL, poly- (N- isopropyl acrylamides), poly-（N- methylol acryloyls
Amine), poly- (N- ［ (2,2- dimethyl-DOX) methyl) acrylamide), poly- (N- (2- hydroxypropyls) methacryl
Amine), poly- (acrylic acid 2- hydroxyl ethyl esters), poly- (2,3- dihydroxypropyl methacrylate), poly- (ether amines), poly-（N- vinylpyridines
Pyrrolidone), poly- (N- caprolactams), poly- (2- oxazolines) and its derivative, poly- (2- (diethylamino) ethyl propylene
Acid esters), poly- (2- (dimethylamino) ethylmethyl acrylate), poly- (2- (diethylamino) ethylmethyl acrylate),
Poly- (2- vinylpyridines), poly- (1- vinyl imidazoles), poly- (N- acryloyl morpholines), poly- (ethyl glycol ester) and by
The copolymer obtained to the monomer of above-mentioned polymer..
The radical initiator is：Azo type free radical initiator, peroxide radical initiator or oxidation are also
Former class initiator.
The solvent is：Amide solvent such as DMF, DMA, hexamethyl phosphinylidyne three
Amine etc., sulfone and sulfoxide type solvents such as dimethyl sulfoxide (DMSO), dimethyl sulfone, sulfolane etc., ether solvent such as tetrahydrofuran, Isosorbide-5-Nitrae-dioxy
Six rings, n-butyl ether etc., ketones solvent such as acetone, butanone, heptanone etc., alcohols solvent such as methanol, ethanol, propyl alcohol, isopropanol, fourth
Alcohol, amylalcohol, hexanol etc., nitrile solvents such as acetonitrile etc., halogenated alkyl solvent such as dichloromethane, chloroform, carbon tetrachloride etc., fragrance
Class solvent such as benzene, α, α, α-benzotrifluoride etc., other common solvents such as 1-METHYLPYRROLIDONE, water etc., and above-mentioned solvent
Mixed solvent.
Brief description of the drawings：
Hydrophilic macromolecule brush is grafted to the process flow diagram flow chart on MIP microballoons using chemical conjugation methods by Fig. 1.
The electron scanning micrograph of the MIP microballoons (using 2,4-D as template) of Fig. 2 surfaces double bond containing C=C.
The scanning of the corresponding non-imprinted polymer microballoon of MIP microballoons (using 2,4-D as template) of Fig. 3 surfaces double bond containing C=C
Electron micrograph.
The surface that Fig. 4 are obtained using chemical conjugation methods has hydrophilic polyglycol polymer brush (Mn=5000)
The electron scanning micrograph of MIP microballoons (using 2,4-D as template molecule).
The surface that Fig. 5 are obtained using chemical conjugation methods has hydrophilic polyglycol polymer brush (Mn=5000)
The electron scanning micrograph of the corresponding non-imprinted polymer microballoon of MIP microballoons (using 2,4-D as template molecule).
The surface that Fig. 6 are obtained using chemical conjugation methods has hydrophily NIPA polymer brush
(Mn,NMRThe electron scanning micrograph of=MIP microballoons (using 2,4-D as template molecule) 10300).
The surface that Fig. 7 are obtained using chemical conjugation methods has hydrophily NIPA polymer brush
(Mn,NMRThe scanning electron microscopy of=corresponding non-imprinted polymer the microballoon of MIP microballoons (using 2,4-D as template molecule) 10300)
Mirror photo.
Fig. 8 surfaces have hydrophilic polyglycol polymer brush (Mn=1000,2000,5000,10000) it is (a) and poly-
(NIPA) polymer brush (MN, NMR=2470,6200,10300,14600) the MIP microballoons of (b) (are with 2,4-D
Template molecule) in methanol/water (4: 1 volume ratio), water, plain chocolate and the selectivity absorption property (suction in pure cow's serum to 2,4-D
Enclosure temperature is 25 DEG C, and 2,4-D concentration is 0.02mM, and MIP and non-imprinted polymer concentration are 16mg/mL).
Fig. 9 surfaces have hydrophilic polyglycol polymer brush (Mn=1000,2000,5000,10000) and poly- (N-
N-isopropylacrylamide) polymer brush (MN, NMR=2470,6200,10300,14600) MIP microballoons (are template point with 2,4-D
Son) and its non-imprinted polymer (CP) microballoon in (a) plain chocolate and (b) pure cow's serum to 2,4-D and the like benzene oxygen second
(adsorption temp is 25 DEG C to the selective absorption performance of sour (POAc), and 2,4-D and POAc concentration is 0.02mM, MIP and CP
Concentration is 16mg/mL).
Embodiment
Example 1
MIP microballoons (double bond content is 0.0408mmol/g) by 150mg using 2,4-D as template, which are added, is equipped with 30mL diformazans
In the eggplant type bottle of base formamide, 0.0736mmol polyethylene glycol Macromolecular chain transfer agent (M is then addedn=5000) and
0.0238mmol azodiisobutyronitrile (AIBN).Jelly seals reaction system after taking out five deoxygenations, is placed in 60 DEG C of constant temperature oil baths
In, 48h is reacted, high speed centrifugation obtains reaction product.
Surface grafting hydrophilic polyglycol macromolecular brush (Mn=non-imprinted polymer microballoon process 5000) is ibid.
Example 2
MIP microballoons (double bond content is 0.0408mmol/g) by 150mg using 2,4-D as template, which are added, is equipped with 30mL diformazans
In the eggplant type bottle of base formamide, 0.0736mmol NIPA Macromolecular chain transfer agent is then added
(Mn,NMR=10300) and 0.0238mmol azodiisobutyronitrile (AIBN).Jelly seals reaction system after taking out five deoxygenations, puts
In 60 DEG C of constant temperature oil baths, 48h is reacted, high speed centrifugation obtains reaction product.
Surface grafting hydrophily NIPA macromolecular brush (Mn,NMR=non-imprinted polymer 10300)
Microballoon process is ibid.
Example 3
MIP microballoons (double bond content is 0.0383mmol/g) by 50mg using inderal as template, which are added, is equipped with 10mL diformazans
In the eggplant type bottle of base formamide, 0.0245mmol polyethylene glycol Macromolecular chain transfer agent (M is then addedn=5000) and
0.0159mmol azodiisobutyronitrile (AIBN).Jelly seals reaction system after taking out five deoxygenations, is placed in 60 DEG C of constant temperature oil baths
In, 48h is reacted, high speed centrifugation obtains reaction product.
Surface grafting hydrophilic polyglycol macromolecular brush (Mn=non-imprinted polymer microballoon process 5000) is ibid.
Example 4
MIP microballoons (double bond content is 0.0383mmol/g) by 50mg using inderal as template, which are added, is equipped with 10mL diformazans
In the eggplant type bottle of base formamide, 0.0245mmol NIPA Macromolecular chain transfer agent is then added
(MN, NMR=10300) and 0.0159mmol azodiisobutyronitrile (AIBN).Jelly seals reaction system after taking out five deoxygenations, puts
In 60 DEG C of constant temperature oil baths, 48h is reacted, high speed centrifugation obtains reaction product.
Surface grafting hydrophily NIPA (Mn,NMR=non-imprinted polymer microballoon process 10300)
Ibid.
Example 5
MIP microballoons (double bond content is 0.0568mmol/g) by 50mg using atenolol as template, which are added, is equipped with 10mL bis-
In the eggplant type bottle of NMF, 0.0245mmol polyethylene glycol Macromolecular chain transfer agent (M is then addedn=10000) and
0.0159mmol azodiisobutyronitrile (AIBN).Jelly seals reaction system after taking out five deoxygenations, is placed in 60 DEG C of constant temperature oil baths
In, 48h is reacted, high speed centrifugation obtains reaction product.
Surface grafting hydrophilic polyglycol macromolecular brush (Mn=non-imprinted polymer microballoon process 10000) is ibid.
Example 6
MIP microballoons (double bond content is 0.0568mmol/g) by 50mg using atenolol as template, which are added, is equipped with 10mL bis-
In the eggplant type bottle of NMF, 0.0245mmol NIPA Macromolecular chain transfer agent is then added
(MN, NMR=14600) and 0.0159mmol azodiisobutyronitrile (AIBN).Jelly seals reaction system after taking out five deoxygenations, puts
In 60 DEG C of constant temperature oil baths, 48h is reacted, high speed centrifugation obtains reaction product.
Surface grafting hydrophily NIPA (Mn,NMR=non-imprinted polymer microballoon process 14600)
Ibid.
Claims (26)
1. a kind of prepare the method that surface has molecularly imprinted polymer (MIP) microballoon of hydrophilic macromolecule brush, it is characterized in that
There is the MIP microballoons of hydrophilic macromolecule brush to be by large hydrophilic molecular chain-transferring agent and surface double bond containing C=C on the surface
MIP microballoons pass through chemical coupling reaction realize.
2. the method that preparation surface according to claim 1 has the MIP microballoons of hydrophilic macromolecule brush, it is characterised in that
Comprise the following steps：
1) MIP microballoons, general radical initiator and the solvent of large hydrophilic molecular chain-transferring agent, surface double bond containing C=C are mixed
It is even, sealed after the oxygen in removing system；
2) reaction system of good seal is reacted at a certain temperature, obtaining surface has the MIP of hydrophilic macromolecule brush
Microballoon.
3. preparation surface according to claim 1 or 2 has the method for the MIP microballoons of hydrophilic macromolecule brush, its feature
It is the hydrophilic polymer with double thioesters or trithio ester terminal to be described large hydrophilic molecular chain-transferring agent.
4. the method that preparation surface according to claim 3 has the MIP microballoons of hydrophilic macromolecule brush, it is characterised in that
Described large hydrophilic molecular chain-transferring agent be selected from polyalcohols, polyurethane, polyacrylamide, polyvinylether, polyester, polyvinylamine,
Polyethyleneimine, polyalkylene oxide, poly- (carboxylic acid), polyamide, polyanhydride, polyphosphazene, polypeptide, fibrin and elastin laminin, polysaccharide,
Albumin, oligopeptides and oligonucleotides and the copolymer obtained by the monomer for obtaining above-mentioned polymer.
5. the method that preparation surface according to claim 4 has the MIP microballoons of hydrophilic macromolecule brush, it is characterised in that
The polyamide is poly- (lactams).
6. the method that preparation surface according to claim 4 has the MIP microballoons of hydrophilic macromolecule brush, it is characterised in that
The polysaccharide is cellulose, heparin, glucan, hyaluronic acid, chitin, alginates.
7. the method that preparation surface according to claim 4 has the MIP microballoons of hydrophilic macromolecule brush, it is characterised in that
The polypeptide is gelatin.
8. the method that preparation surface according to claim 4 has the MIP microballoons of hydrophilic macromolecule brush, it is characterised in that
The polyalcohols is polyvinyl alcohol.
9. the method that preparation surface according to claim 4 has the MIP microballoons of hydrophilic macromolecule brush, it is characterised in that
Poly- (carboxylic acid) is poly- (methyl) acrylic acid.
10. the method that preparation surface according to claim 3 has the MIP microballoons of hydrophilic macromolecule brush, its feature exists
Polyethylene glycol, poly-N-isopropyl acrylamide, polymethylacrylic acid 2- hydroxyls are selected from described large hydrophilic molecular chain-transferring agent
Base ethyl ester, poly- (methyl) acrylamide, poly- N, N '-DMAA, polymethylacrylic acid dimethylamino ethyl ester, poly- ([2-
(methacryloxy) ethyl] dimethyl-(3- sulfopropyls) ammonium hydroxide), it is poly- (3-2-N- methylacryoyloxyethyl-N,
N- dimethyl propyl sulfonic acids amine), poly- (2- methylacryoyloxyethyls phosphocholine), (oxygen (11- (3- sulfonyl propyl group front threes
Base-glycidyl) hendecane base ester sulphomethyl) ethene-epoxide (dodecyl sulphomethyl) ethene) it is copolymer, poly-
(acrylamido -2- methyl isophthalic acids-propane sulfonic acid), poly- (methacryloylethyl sulfobetaines), poly- (methylacryoyloxyethyl
Trimethyl ammonium chloride), poly- (4- [dimethyl (2 '-methacryloxyethyl) ammonium] butyrate), poly- (methacrylic acid 3- sulphurs
Methacrylate potassium salt), poly- (methyl methacrylate sulfobetaines), poly- (Methacrylamide sulfobetaines), poly- (styrene
Sulfonate), poly- (styrene sulfonic acid), polyacrylic acid, polymethyl propylhomoserin sodium, methoxyl group three (ethylene glycol) methacrylic acid
Ester-methacrylic acid copolymer, PEG methyl ether methacrylate, poly- (methacrylic acid oxyethylene glycol ester), poly-
(sarcosine), PLGA, PLL, poly- (N- isopropyl acrylamides), poly- (N- methylols
Acrylamide), poly- (N- [(2,2- dimethyl -1,3- dioxolanes) methyl) acrylamide), poly- (N- (2- hydroxypropyls) methyl-prop
Acrylamide), poly- (acrylic acid 2- hydroxyl ethyl esters), poly- (2,3- dihydroxypropyls methacrylate), poly- (ether amines), poly- (N- ethene
Base pyrrolidones), poly- (N- caprolactams), poly- (2- oxazolines) and its derivative, poly- (2- (diethylamino) ethyl
Acrylate), poly- (2- (dimethylamino) ethylmethyl acrylate), poly- (2- (diethylamino) ethyl methacrylate
Ester), poly- (2- vinylpyridines), poly- (1- vinyl imidazoles), poly- (N- acryloyl morpholines), poly- (ethyl glycol ester) and
The copolymer obtained by the monomer for obtaining above-mentioned polymer.
11. the method that preparation surface according to claim 10 has the MIP microballoons of hydrophilic macromolecule brush, its feature exists
In the PEG methyl ether methacrylate be poly- (low PEG methyl ether methacrylate).
12. preparation surface according to claim 1 or 2 has the method for the MIP microballoons of hydrophilic macromolecule brush, its feature
The MIP microballoons for being described surface double bond containing C=C are modified by various precipitation polymerization process and by MIP microsphere surfaces
Introduce prepared by C=C double bonds.
13. preparation surface according to claim 1 or 2 has the method for the MIP microballoons of hydrophilic macromolecule brush, its feature
Surface C=C the double bond contents for being the MIP microballoons of described surface double bond containing C=C are 0.005~0.50 mM/gram.
14. the method that preparation surface according to claim 2 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
Described general radical initiator is azo type free radical initiator, peroxide radical initiator or redox class
Initiator.
15. the method that preparation surface according to claim 2 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The solvent is amide solvent, sulfone and sulfoxide type solvents, ether solvent, ketones solvent, alcohols solvent, nitrile solvents, halo
Alkane solvents, aromatic solvents, HMPA, the mixed solvent of water and above-mentioned solvent.
16. the method that preparation surface according to claim 15 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The amide solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide.
17. the method that preparation surface according to claim 15 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The sulfone and sulfoxide type solvents are dimethyl sulfoxide (DMSO), dimethyl sulfone, sulfolane.
18. the method that preparation surface according to claim 15 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The ether solvent is tetrahydrofuran, 1,4- dioxane, n-butyl ether.
19. the method that preparation surface according to claim 15 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The ketones solvent is acetone, butanone, heptanone, 1-METHYLPYRROLIDONE.
20. the method that preparation surface according to claim 15 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The alcohols solvent is methanol, ethanol, propyl alcohol, butanol, amylalcohol, hexanol.
21. the method that preparation surface according to claim 15 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The alcohols solvent is isopropanol.
22. the method that preparation surface according to claim 15 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The nitrile solvents are acetonitriles.
23. the method that preparation surface according to claim 15 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The halogenated alkyl solvent is dichloromethane, chloroform, carbon tetrachloride.
24. the method that preparation surface according to claim 15 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The aromatic solvents are benzene, α, α, α-benzotrifluoride.
25. the method that preparation surface according to claim 2 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The MIP microballoons of described surface double bond containing C=C, large hydrophilic molecular chain-transferring agent, general radical initiator, the use of solvent
Amount is as follows：
1) the MIP microballoons of surface double bond containing C=C and the ratio of large hydrophilic molecular chain-transferring agent according to MIP microsphere surfaces C=
C double bonds and the mol ratio 1 of large hydrophilic molecular chain-transferring agent:1~100 calculates consumption；
2) mol ratio of general radical initiator and large hydrophilic molecular chain-transferring agent is 1:0.15~30；
3) solvent and the MIP microballoons amount ratio of surface double bond containing C=C are 0.04~2 liter/gram.
26. the method that preparation surface according to claim 2 has the MIP microballoons of hydrophilic macromolecule brush, it is characterized in that
The temperature is 25~200 DEG C, and the time of the reaction is 1~500 hour.
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| CN106700086B (en) * | 2016-11-22 | 2019-06-11 | 鲁东大学 | A kind of preparation method for the polymer brush can be used for chemical-biological sensing |
| WO2019163764A1 (en) * | 2018-02-20 | 2019-08-29 | テルモ株式会社 | Medical instrument |
| CN109065744B (en) | 2018-07-10 | 2020-03-17 | 武汉华星光电半导体显示技术有限公司 | OLED display panel and packaging method thereof |
| CN109666403A (en) * | 2018-12-28 | 2019-04-23 | 东南大学苏州医疗器械研究院 | Anti-adhesive coating composition and anti-adhesive coating |
| CN111574720B (en) * | 2019-02-18 | 2022-06-17 | 南开大学 | Preparation method of molecularly imprinted polymer microspheres suitable for complex water sample analysis |
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| CN102952236A (en) * | 2011-08-29 | 2013-03-06 | 南开大学 | Molecularly imprinted polymeric microsphere resin applicable to aqueous solution system and preparing method thereof |
| CN102492250A (en) * | 2011-12-08 | 2012-06-13 | 天津工业大学 | Temperature-sensitive polymer/gold nanoparticle hybrid microspheres and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| "Efficient synthesis of narrowly dispersed hydrophilic and magnetic molecularly imprinted polymer microspheres with excellent molecular recognition ability in a real biological sample";Man Zhao, et al.;《Chemical Communications》;20131223;第50卷(第17期);第2208-2210页 * |
| "谷胱甘肽/壳聚糖复合物的合成及在药物载体上的应用";李从欣;《中国硕士学位论文全文数据库》;20111231;第1章第3节，第2章第2.2.3.2节 * |
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