CN1390863A - Magnetic composite microsphere of molecular blot polymer and its suspemsion polymerization process for preparing it - Google Patents
Magnetic composite microsphere of molecular blot polymer and its suspemsion polymerization process for preparing it Download PDFInfo
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Abstract
A composite magnetic microsphere of molecular blot polymer, based on molecular blot technique, is prepared from different substances as template (or blot) molecule, different monomers as functional monomer and the mother material of polymer and different metals (or their oxides) as magnetic component through suspension polymerization. It can be used for separating similar compound, chiral compound, by-product and trace compound with more accuracy and simple process.
Description
Technical field
The invention belongs to Materials Science and Engineering and bioseparation engineering field, more precisely relate to a kind of magnetic composite microsphere of molecular blot polymer and suspension polymerization preparation method thereof.
Background technology
Molecular imprinting in a lot of fields, obtain extensive and deep research such as a lot of aspects such as the separation of analogue compounds, antibodies simulation, enzyme simulation, biosimulation transmitter, become one of novel material of tool potentiality of new millennium with the molecularly imprinted polymer (MIPs) of this technology preparation.
MIPs is in early days with mass polymerization preparation (Wulff G.Molecular recognition inpolymers prepared by imprinting with template, polymeric reagents andcatalytics, Am Chem Soc Sym Ser, 1986,308 (2): 186-200).Though this method polymerization process is very simple, last handling process is very loaded down with trivial details, must just can finish through processes such as the template molecule wash-out of (also claiming microsphere), grinding, screenings, and is not only consuming time, and the particle that obtains is irregular, and productive rate has only about 20% simultaneously.And employing suspension polymerization (Berglund J, Nicholls I A, Lindbladh C.Recognition in molecularly imprinte polymer-adrenoreceptor mimics, Bioorg Med chem Lett, 1996,6 (18): 2237-2242) can directly prepare spherical molecularly imprinted polymer (SMIPs), and need only just can directly use through the wash-out of template molecule.Because many characteristics such as SMIPs has that shape is regular, specific surface is big, high adsorption capacity, particle diameter can be adjusted as required, and have good chemical stability and stability in storagies such as physicals such as anti-machinery, high temperature high voltage resistant and antiacid alkali, anti-multiple organic solvent, therefore, be suitable as very much parting material.
Be used for the molecular blotting polymer microsphere in separation engineering field at present owing to do not contain magnetic component and can't carry out simply and separate easily with magnetic field, can only carry out static separation (D Wistuba, V Schurig.Enantiomer separation of chiral pharmaceuticals by capillaryelectrochromatography, Journal of Chromatography A, 2000,875:255-276); If carry out dynamic separation, then need to separate SMIPs through process such as centrifugal, operating process is loaded down with trivial details, complicated.
When imbedding the magnetic responsiveness material in polymer microballoon inside, during as iron, cobalt, nickel or its oxide compound, complex microsphere then has and is adding easy under the action of a magnetic field, magnetic stalling characteristic (C Bor Fuh fast, S Y Chen.Magnetic split-flow thin fractionation:new technique for separation ofmagnetically susceptible particles, Journal of Chromatography A, 1998,813:313-324).After in SMIPs, imbedding the magnetic responsiveness material, just can finish " initiatively " of template molecule absorption added under the action of a magnetic field with the identification back being easy to it is separated at it, reach initiatively identification and convenient isolating purpose.
The present invention is intended to by suspension polymerization molecular imprinting be combined with magnetic susceptibility, give molecular blotting polymer microsphere certain magnetic responsiveness, make the magnetic composite microsphere of molecular blot polymer that makes finish " initiatively " absorption to template molecule and adding under the action of a magnetic field with specificity identification back and be easy to it is separated, reach initiatively identification and convenient isolating purpose at it.
Summary of the invention
Technology of the present invention is the compatibility problem that solves metal (or its oxide compound) and polymkeric substance, realize the embedding of polymkeric substance to inorganics, thereby give polymer microballoon certain magnetic responsiveness, and finish the trace process of template molecule simultaneously, make magnetic composite microsphere have singleness identity, reach the purpose of particular separation template molecule.
The present invention is according to the principle of molecular imprinting, with different materials as template molecule (microsphere), different monomers is as function monomer and polymeric matrix material, different metal (or its oxide compound) is as magnetic component, saturated fatty acid is a pore-creating agent, macromolecule stabilizer is a dispersion agent, adopts suspension polymerization to make the magnetic composite microsphere of molecular blot polymer that template molecule is had singleness identity.
This microballoon is to be compounded with the magnetic response material in molecular blotting polymer microsphere, has many holes on polymer microballoon.
The invention process method is as follows:
A. use ultrasonic dispersing 5～60min in the aqueous solution of adding macromolecule stabilizer after magnetic powder being ground, adding has in the reactor of agitator, reflux exchanger, ventpipe; Initiator and pore-creating agent are added in the monomer, add in the reactor respectively after the dissolving, and start stirring; Template molecule is added adding function monomer in dissolving back in the entry, add in the reactor behind stirring 5～60min, continue to stir; Be warmed up to 50～90 ℃ then, and logical nitrogen replacement deoxygenation; After reaction finished, the filtering aqueous portion obtained magnetic composite microsphere of molecular blot polymer;
B. the magnetic composite microsphere of molecular blot polymer of preparation is poured in the reactor after with distilled water wash, add 50～200m1 water, be heated to 30～90 ℃ then, drip 0.1～2mol/L NaOH solution, 5～100ml, stir and be incubated 5～60min, cooling is filtered then; Wash with water after the filtration, soak 2～48h with 0.1～10% acetum, 20～100ml again, wash repeatedly to neutrality with distilled water behind the elimination acetum, be dried to constant weight in 40～90 ℃ with vacuum drying oven then.
Wherein:
Magnetic powder is: Fe, Co, Ni or its oxide compound or its alloy;
Macromolecule stabilizer is: polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, Natvosol,
Hydroxypropylcellulose, polyacrylic acid and dextrin;
Initiator is: Diisopropyl azodicarboxylate, benzoyl peroxide, hydrogen phosphide cumene and dicumyl peroxide;
Pore-creating agent is: saturated fatty acids such as lauric acid, palmitinic acid, stearic acid;
Monomer is: vinylbenzene, divinylbenzene, methyl methacrylate, vinyl cyanide, Ethylene glycol dimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane three CALCIUM ACRYLATE;
Template molecule is: water-soluble organic compounds such as amino acid and derivative thereof, chipal compounds, medicine, sterilant, dyestuff;
Function monomer is: methacrylic acid, vinylformic acid, acrylamide, N, N '-methylene-bisacrylamide.
Magnetic composite microsphere of molecular blot polymer of the present invention combines the accurate specificity evident characteristics of molecularly imprinted polymer and magnetic composite microsphere foreign field stalling characteristic dual-use function easily, will be at many separation fields, have broad application prospects as aspects such as the separation of the separation of the separation of the separation of analogue compounds, chipal compounds, by product, trace compound and enrichments, and loaded down with trivial details in the past sepn process (as high speed centrifugation etc.) is simplified greatly.And existing be used for the molecular blotting polymer microsphere in separation engineering field owing to do not contain magnetic component and can't carry out simply and separate easily with magnetic field; Existing magnetic composite microsphere can not be realized accurate separation owing to do not have the specificity recognition function without molecular imprinting.
Pore is convenient owing to having added in the polymerization process, removal is easy to the saturated fatty acid pore-creating agent in the present invention, makes that prepared complex microsphere is a porous microsphere, has increased microballoon specific surface area and loading capacity, has increased the rate of mass transfer of template molecule in microballoon.
Description of drawings Fig. 1: embodiment 1 prepared porous magnetic composite microsphere of molecular blot polymer (median size 440 μ m,
Aperture about 5) μ m, Fe
3O
4Content 3.78%) Fig. 2: embodiment 2 prepared porous magnetic composite microsphere of molecular blot polymer (median size 460 μ m,
The about 3 μ m in aperture, Fe
3O
4Content 2.76%)
Embodiment
Embodiment 1.
With Fe
3O
4Powder adds after grinding in the aqueous solution of Macrogol 4000 (PEG4000) uses ultrasonic dispersing 30min, adds in the there-necked flask of the 250ml that has agitator, reflux exchanger, ventpipe; Diisopropyl azodicarboxylate (AIBN) and stearic acid (SA) are added in the mixture of vinylbenzene (St) and divinylbenzene (DVB), add in the there-necked flask respectively after the dissolving, and start stirring; Tyrosine (Tyr) is added dissolving back adding methacrylic acid (MAA) and acrylamide (AM) in the entry, add in the there-necked flask behind the stirring 30min, continue to stir.Heat up then, and logical nitrogen 5min displacement deoxygenation; 70 ℃ of control reaction temperature, reaction 24h.With 180 eye mesh screen filtering aqueous portions, obtain the magnetic molecularly imprinted polymer complex microsphere.
The magnetic composite microsphere of molecular blot polymer of preparation is poured in the 500ml flask with behind the distilled water flushing three times, added 150ml water, be heated to 70 ℃ then, drip 1M NaOH solution 10ml, stir also insulation 30min, cooling filtration then.Wash with water after the filtration three times, soak 24h with 1% acetum 100ml again, wash repeatedly to neutrality with distilled water behind the elimination acetum, be dried to constant weight in 80 ℃ with vacuum drying oven then.
The prescription Fe of table 1 suspension polymerization magnetic composite microsphere of molecular blot polymer
3O
4Tyr MAA AM St DVB PEG SA AIBN H
2O (g) is (mmol) (mmol) (g) (g) (g) (mmol) (g) (ml) 0.8 2 20 20 15 5 20 2 0.2 150 (mmol)
Prepared magnetic composite microsphere of molecular blot polymer is to be compounded with Fe in the tyrosine molecular blotting polymer microsphere
3O
4Magneticsubstance, Fe
3O
4Content is 3.78%, and the aperture is about 5 μ m, is the contrast molecule with the phenylalanine, and its separation factor to tyrosine is 3.67.
Embodiment 2.
With Fe
3O
4Powder adds after grinding in the aqueous solution of polyethylene glycol 6000 (PEG6000) uses ultrasonic dispersing 30min, adds in the there-necked flask of the 250ml that has agitator, reflux exchanger, ventpipe; Diisopropyl azodicarboxylate (AIBN) and lauric acid (LA) are added in the mixture of trimethylolpropane triacrylate (TRIM) and toluene (Tolu), add in the there-necked flask respectively after the dissolving, and start stirring; Phenylalanine (Phe) is added adding methacrylic acid (MAA) in dissolving back in the entry, add in the there-necked flask behind the stirring 30min, continue to stir.Heat up then, and logical nitrogen 5min displacement deoxygenation; 70 ℃ of control reaction temperature, reaction 10h.After finishing, reaction is warming up to 85 ℃ and vacuumize 30min.With 180 eye mesh screen filtering aqueous portions, obtain the magnetic molecularly imprinted polymer complex microsphere.
The magnetic composite microsphere of molecular blot polymer of preparation is poured in the 500ml flask with behind the distilled water flushing three times, added 150ml water, be heated to 70 ℃ then, drip 1M NaOH solution 10ml, stir also insulation 30min, cooling filtration then.Wash with water after the filtration three times, soaked 24 hours with 1% acetum 100ml again, wash repeatedly to neutrality with distilled water behind the elimination acetum, be dried to constant weight in 80 ℃ with vacuum drying oven then.
The prescription Fe of table 2 suspension polymerization magnetic composite microsphere of molecular blot polymer
3O
4Phe MAA TRIM PEG LA Tolu AIBN H
2O (g) is (mmol) (g) (g) (mmol) (ml) (g) (ml) 0.8 2 20 20 20 25 0.2 150 (mmol)
Prepared magnetic composite microsphere of molecular blot polymer is to be compounded with Fe in the phenylalanine molecular blotting polymer microsphere
3O
4Magneticsubstance, Fe
3O
4Content is 2.76%, and the aperture is about 3 μ m, is the contrast molecule with tyrosine, and its separation factor to phenylalanine is 2.08.
Embodiment 3.
With Fe
2O
3Powder adds after grinding in the aqueous solution of Natvosol (HEC) uses ultrasonic dispersing 30min, adds in the there-necked flask of the 250ml that has agitator, reflux exchanger, ventpipe; Benzoyl peroxide (BPO) and palmitinic acid (CA) are added in the mixture of tetramethylolmethane three CALCIUM ACRYLATE (PETRA) and benzene (Ben), add in the there-necked flask respectively after the dissolving, and start stirring; With tryptophane () add in the entry dissolving back and add methacrylic acid (MAA), N, N '-methylene-bisacrylamide (Bis) adds in the there-necked flask after stirring 30min, continues to stir.Heat up then, and logical nitrogen 5min displacement deoxygenation; 70 ℃ of control reaction temperature, reaction 12h.After finishing, reaction is warming up to 85 ℃ and vacuumize 30min.With 180 eye mesh screen filtering aqueous portions, obtain the magnetic molecularly imprinted polymer complex microsphere.
The magnetic composite microsphere of molecular blot polymer of preparation is poured in the 500ml flask with behind the distilled water flushing three times, added 150ml water, be heated to 70 ℃ then, drip 1M NaOH solution 10ml, stir also insulation 30min, cooling filtration then.Wash with water after the filtration three times, soaked 24 hours with 1% acetum 100ml again, wash repeatedly to neutrality with distilled water behind the elimination acetum, be dried to constant weight in 80 ℃ with vacuum drying oven then.
The prescription Fe of table 3 suspension polymerization magnetic composite microsphere of molecular blot polymer
2O
3Trp MAA Bis PETRA HEC CA Ben BPO H
2O (g) is (mmol) (mmol) (g) (g) (mmol) (ml) (g) (ml) 0.8 2 20 20 20 525 0.2 150 (mmol)
Prepared magnetic composite microsphere of molecular blot polymer is to be compounded with Fe in the tryptophane molecular blotting polymer microsphere
2O
3Magneticsubstance, Fe
3O
4Content is 2.35%, and the aperture is about 5 μ m, is the contrast molecule with tyrosine, and its separation factor to tryptophane is 2.89.
Claims (9)
1. a magnetic composite microsphere of molecular blot polymer is characterized in that being compounded with the magnetic response material in molecular blotting polymer microsphere, has many holes on polymer microballoon.
2. a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 1 is characterized in that being compounded with Fe in the tyrosine molecular blotting polymer microsphere
3O
4Magneticsubstance, Fe
3O
4Content is 3.78%, and the aperture is about 5 μ m, is the contrast molecule with the phenylalanine, and its separation factor to tyrosine is 3.67.
3. a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 1 is characterized in that being compounded with Fe in the phenylalanine molecular blotting polymer microsphere
3O
4Magneticsubstance, Fe
3O
4Content is 2.76%, and the aperture is about 3 μ m, is the contrast molecule with tyrosine, and its separation factor to phenylalanine is 2.08.
4. a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 1 is characterized in that being compounded with Fe in the tryptophane molecular blotting polymer microsphere
2O
3Magneticsubstance, Fe
3O
4Content is 2.35%, and the aperture is about 5 μ m, is the contrast molecule with tyrosine, and its separation factor to tryptophane is 2.89.
5. the suspension polymerization preparation method of a magnetic composite microsphere of molecular blot polymer may further comprise the steps:
A. use ultrasonic dispersing 5～60min in the aqueous solution of adding macromolecule stabilizer after magnetic powder being ground, adding has in the reactor of agitator, reflux exchanger, ventpipe; Initiator and pore-creating agent are added in the monomer, add in the reactor respectively after the dissolving, and start stirring; Template molecule is added adding function monomer in dissolving back in the entry, add in the reactor behind stirring 5～60min, continue to stir; Be warmed up to 50～90 ℃ then, and logical nitrogen replacement deoxygenation; After reaction finished, the filtering aqueous portion obtained magnetic composite microsphere of molecular blot polymer;
B. the magnetic composite microsphere of molecular blot polymer of preparation is poured in the reactor after with distilled water wash, add 50～200ml water, be heated to 30～90 ℃ then, drip 0.1～2mol/L NaOH solution, 5～100ml, stir and be incubated 5～60min, cooling is filtered then; Wash with water after the filtration, soak 2～48h with 0.1～10% acetum, 20～100ml again, wash repeatedly to neutrality with distilled water behind the elimination acetum, be dried to constant weight in 40～90 ℃ with vacuum drying oven then.
6. the suspension polymerization preparation method of a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 5, it is characterized by described: magnetic powder is: Fe, Co, Ni or its oxide compound or its alloy; Macromolecule stabilizer is: polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, Natvosol, hydroxypropylcellulose, polyacrylic acid and dextrin; Initiator is: Diisopropyl azodicarboxylate, benzoyl peroxide, hydrogen phosphide cumene and dicumyl peroxide; Pore-creating agent is: saturated fatty acids such as lauric acid, palmitinic acid, stearic acid, and monomer is: vinylbenzene, divinylbenzene, methyl methacrylate, vinyl cyanide, Ethylene glycol dimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane three CALCIUM ACRYLATE; Template molecule is: water-soluble organic compounds such as amino acid and derivative thereof, chipal compounds, medicine, sterilant, dyestuff; Function monomer is: methacrylic acid, vinylformic acid, acrylamide, N, N '-methylene-bisacrylamide.
7. the suspension polymerization preparation method of a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 5 may further comprise the steps:
A) with Fe
3O
4Powder adds after grinding in the aqueous solution of Macrogol 4000 uses ultrasonic dispersing 30min, adds in the there-necked flask of the 250ml that has agitator, reflux exchanger, ventpipe; Diisopropyl azodicarboxylate and stearic acid are added in the mixture of vinylbenzene and divinylbenzene, add in the there-necked flask respectively after the dissolving, and start stirring; Tyrosine is added dissolving back adding methacrylic acid and acrylamide in the entry, add in the there-necked flask behind the stirring 30min, continue to stir; Heat up then, and logical nitrogen 5min displacement deoxygenation; 70 ℃ of control reaction temperature, reaction 24h; With 180 eye mesh screen filtering aqueous portions, obtain the magnetic molecularly imprinted polymer complex microsphere;
B) magnetic composite microsphere of molecular blot polymer of preparation is poured in the 500ml flask with behind the distilled water flushing three times, added 150ml water, be heated to 70 ℃ then, drip 1M NaOH solution 10ml, stir also insulation 30min, cooling filtration then; Wash with water after the filtration three times, soak 24h with 1% acetum 100ml again, wash repeatedly to neutrality with distilled water behind the elimination acetum, be dried to constant weight in 80 ℃ with vacuum drying oven then.
8. the suspension polymerization preparation method of a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 7 is characterized in that described step a) is:
With Fe
3O
4Powder adds after grinding in the aqueous solution of polyethylene glycol 6000 uses ultrasonic dispersing 30min, adds in the there-necked flask of the 250ml that has agitator, reflux exchanger, ventpipe; Diisopropyl azodicarboxylate and lauric acid are added in the mixture of trimethylolpropane triacrylate and toluene, add in the there-necked flask respectively after the dissolving, and start stirring; Phenylalanine is added adding methacrylic acid in dissolving back in the entry, add in the there-necked flask behind the stirring 30min, continue to stir; Heat up then, and logical nitrogen 5min displacement deoxygenation; 70 ℃ of control reaction temperature, reaction 10h; After finishing, reaction is warming up to 85 ℃ and vacuumize 30min; With 180 eye mesh screen filtering aqueous portions, obtain the magnetic molecularly imprinted polymer complex microsphere.
9. the suspension polymerization preparation method of a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 7 is characterized in that described step a) is:
With Fe
2O
3Powder adds after grinding in the aqueous solution of Natvosol uses ultrasonic dispersing 30min, adds in the there-necked flask of the 250ml that has agitator, reflux exchanger, ventpipe; Benzoyl peroxide and palmitinic acid are added in the mixture of tetramethylolmethane three CALCIUM ACRYLATE and benzene, add in the there-necked flask respectively after the dissolving, and start stirring; Tryptophane is added dissolving back adding methacrylic acid, N in the entry, and N '-methylene-bisacrylamide adds in the there-necked flask behind the stirring 30min, continues to stir; Heat up then, and logical nitrogen 5min displacement deoxygenation; 70 ℃ of control reaction temperature, reaction 12h; After finishing, reaction is warming up to 85 ℃ and vacuumize 30min; With 180 eye mesh screen filtering aqueous portions, obtain the magnetic molecularly imprinted polymer complex microsphere.
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| CN104140487B (en) * | 2014-07-22 | 2017-02-22 | 中国科学院烟台海岸带研究所 | Method for preparing estradiol molecularly imprinted magnetic microsphere |
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