CN100395851C - Size controllable molecular engram polymer magnetic composite nano particles and producing process thereof - Google Patents
Size controllable molecular engram polymer magnetic composite nano particles and producing process thereof Download PDFInfo
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- CN100395851C CN100395851C CNB200510018065XA CN200510018065A CN100395851C CN 100395851 C CN100395851 C CN 100395851C CN B200510018065X A CNB200510018065X A CN B200510018065XA CN 200510018065 A CN200510018065 A CN 200510018065A CN 100395851 C CN100395851 C CN 100395851C
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Abstract
The present invention relates to a size controllable molecularly imprinted polymer magnetic composite nanometer particle and a preparation method thereof. The nanometer particle has a polymer shell which has a single recognition capability to template molecules and a core of a nanometer dimension. The present invention is characterized in that the core of the nanometer particle is magnetic nanometer powder; the dimension of the polymer shell is controlled by the reaction time of atom transfer radical polymerization. The present invention has the method that the surface of the magnetic nanometer powder is connected with reaction initiating agents of the atom transfer radical polymerization firstly; the reaction of the atom transfer radical polymerization is initiated under the action of catalyst, and simultaneously, the reaction of molecularly imprinted polymerization happens; a polymer layer containing template molecules is formed at the surface of the magnetic nanometer powder; the size controllable molecularly imprinted polymer magnetic composite nanometer particle is obtained after eluted by the template molecules. The particle can be used for the relative field of the separation of analogue compounds, the separation and the enrichment of trace amount compounds, the catalysis of mimic enzyme, sensors, medicine, etc.
Description
Technical field
The invention belongs to the nano particle new material, relate to a kind of size controllable molecular engram polymer magnetic composite nano particles and preparation method thereof or rather.
Background technology
Molecular imprinting is to collect the frontier branch of science branch that numerous branch superiorities such as Polymer Synthesizing, MOLECULE DESIGN, molecular recognition, bionical bioengineering grow up in recent years.Molecularly imprinted polymer (Molecularly ImprintedPolymers, MIPs) promptly have the recognition performance same with natural antibody, have the high stability same again with macromolecule, thereby be widely used in various fields such as bioengineering, clinical medicine, environmental monitoring, food industry, become new century one of the most potential new material.
The preparation of molecularly imprinted polymer great majority at present prepares method (the Wulff G.Molecularrecognition in polymers by imprinting with template that adopts the tube sealing polymerization, polymeric reagents andcatalytics, Am.Chem.Soc.Sym.Ser., 1986,308 (2): 186-200).Being about to microsphere, function monomer, crosslinking agent and initator is dissolved in the atent solvent (normally chloroform or toluene) by a certain percentage, move into then in the glass ampere bottle, adopt ultrasonic degas, logical nitrogen deoxygenation, at vacuum lower seal ampere bottle, obtain bulk polymer through heat initiation (60～120 ℃) or UV-irradiation (at room temperature wavelength is generally 366nm) initiated polymerization certain hour (normally 24h).Through the particle of processes such as pulverizing, grinding, screening acquisition modest size, wash-out is removed template molecule, after vacuumize.The subject matter of its existence is: 1.. preliminary treatment formalities such as the pulverizing of polymer, grinding, screening are loaded down with trivial details, and the polymer particle uniformity that finally obtains is relatively poor, preparation rate also lower (be total amount about 50%).2.. because the highly crosslinkable and the size of network are bigger, causing template to be difficult to remove, is totally unfavorable for cost control.And the suspension polymerisation that new development is got up (Berglund J., Nicholls I.A., Lindbladh C.Recognition inmolecularly imprinte polymer-adrenoreceptor mimics, Bioorg.Med.Chem.Lett., 1996,6 (18): 2237-2242), then can directly prepare spherical molecular engram nano particle, only need just can directly use through the wash-out of template molecule.The prepared molecularly imprinted polymer of this method has many performances such as shape is regular, specific surface big, high adsorption capacity, anti-mechanicalness, high temperature high voltage resistant, anti-multiple organic solvent, antiacid alkali, good application prospects is arranged, but still exist the MIPs particle size bigger and wayward, the problem that template molecule is difficult to remove.
Key is the molecularly imprinted polymer nano particle that makes at present, and size bigger and uncontrollable (general diameter reaches dozens or even hundreds of nanometer) causes template molecule to be difficult to remove.Can't not carry out simple and processing easily with magnetic field because nano particle does not contain magnetic components in addition, can only carry out static separation, its operating process be loaded down with trivial details, complicated.Molecularly imprinted polymer shortage magnetic responsiveness has also limited it and has used widely.
Summary of the invention
The present invention aims to provide a kind of size controllable molecular engram polymer magnetic composite nano particles and preparation method thereof, to remedy the deficiency of prior art.
Technical conceive of the present invention is polymer nano granules shell controllable size microsphere to be had single-minded recognition capability by molecular imprinting being combined with atom transition free radical polymerization reaction, making, makes polymer have magnetic responsiveness simultaneously.Make the molecularly imprinted polymer nano particle reach specific purpose, with the application prospect of expansion molecularly imprinted polymer.
Therefore, composite nanometer particle of the present invention comprises that template molecule is had the polymer shell of single-minded recognition capability and the nuclear of nano particle, it is characterized in that the polymer shell is the imprinted polymer layer of controllable size, and the nuclear of nano particle is magnetic nanometer powder.The size of imprinted polymer shell is that the nuclear of nano particle is MnFe by the control of atom transition free radical polymerization reaction time
2O
4, Fe
3O
4Perhaps Fe
2O
3Magnetic material.
Method of the present invention is: at first connect the atom transition free radical polymerization reaction initator on the magnetic nanometer powder surface, under the effect of catalyst, cause atom transition free radical polymerization reaction (the molecular engram polymerization reaction takes place simultaneously), form the polymeric layer that comprises template molecule on the magnetic nanometer powder surface, obtain size controllable molecular engram polymer magnetic composite nano particles through the template molecule wash-out.
Concrete grammar of the present invention is as follows:
A. imprinted templates molecule
(1) magnetic nanometer powder is joined in the aqueous solution that the ATRP initiator concentration is 0.5～2mol/L, the ultrasonic dispersion of water-bath did not have precipitation to solution in 5～120 minutes and exists; In above-mentioned solution, add hydrochloric acid and make the pH value maintain 4～6, and be transferred in the reactor that has blender, stirred 1～72 hour; Stirring stops the back centrifugation, obtains the magnetic nanoparticle powder of initator functionalization, is washed with water to neutral and dry;
(2) the magnetic nanoparticle of functionalization adds in the reactor, adds function monomer, template molecule, crosslinking agent successively, stirs to make it to dissolve fully, obtains translucent viscous solution A;
(3) in the another one reactor, united catalyst added to stir in the pore-foaming agent and make it to dissolve fully, add solution A then and mix, obtain solution B;
(4) the logical nitrogen of solution B is 1～60 minute, removes deoxidation and moisture; Reactor places 50～120 ℃ oil bath then, and stirring reaction 1～72 hour can obtain the nano particle of different size, short more size of time more little (being that the imprinted polymer shell is thin more) by control time length; Centrifugation obtains containing the imprinted polymer magnetic composite nano particle of template molecule;
B. wash-out template molecule
The imprinted polymer magnetic composite nano particle that contains template molecule that (1) will prepare, being dispersed to solution with the chloroform of 5～100mL does not have precipitation and exists; Add methyl alcohol 5～100mL then, stirred centrifugation afterwards 5～120 minutes;
(2) centrifugal gained solid is that 10/1～1/10 mixed solution soaks with acetate/methyl alcohol volume ratio, vibrates 1～72 hour; Use the methyl alcohol cyclic washing until neutrality after the elimination soak, in 50～120 ℃, be dried to constant weight then, promptly obtain size controllable molecular engram polymer magnetic composite nano particles with vacuum drying oven.
Wherein above-mentioned:
Magnaglo is: Fe, Co, Ni, Mn or its oxide or its alloy;
Initator is: halopropanoic acid, halogenated acetic acids, 2 bromo 2 methyl propionic acid (BMPA);
Pore-foaming agent is: benzene and derivative thereof, halide, oxolane (THF), N, dinethylformamide (DMF), methyl-sulfoxide (DMSO);
Template molecule is: compounds such as amino acid and derivative thereof, chipal compounds, medicine, agricultural chemicals;
Function monomer is: acrylic acid with and ester class, vinylpyridine class;
Crosslinking agent is: ethylene glycol dimethacrylate (EGDMA), divinylbenzene (DVB);
United catalyst is: cuprous halide and company's arsenic pyridine class united catalyst.
The molecular engram polymer magnetic composite nano particles of shell/nuclear structure of the present invention combines the molecularly imprinted polymer specific recognition ability, the triple characteristics of the controllability of the magnetic responsiveness of magnetic composite nano particle and ATRP technology will have application prospect widely as association areas such as the separation of the separation of analogue compounds, trace compound and enrichment, mimetic enzyme catalysis, transducer, medical science in a lot of fields.
Embodiment
Embodiment 1.
A. imprinted templates molecule
(1) with MnFe
2O
4It is in the aqueous solution of 1mol/L that magnetic powder nanometer powder (9nm) 25mg joins the concentration that contains initator 3-chloropropionic acid, and the ultrasonic dispersion of water-bath 10 minutes obtains the solution of little Huang; In above-mentioned solution, add hydrochloric acid and make the pH value maintain 4, and be transferred in the reactor that has blender, stirred 1 hour; Stirring stops the back centrifugation, obtains the magnetic nanoparticle of yellowish 3-chloropropionic acid functionalization, is washed with water to neutral and dry;
(2) the magnetic nanoparticle of 3-chloropropionic acid functionalization adds in the reactor, adds function monomer methacrylic acid 1mmol, template molecule theophylline 20mg, crosslinking agent EGDMA 5mmol successively, stirs to make it to dissolve fully, obtains translucent viscous solution A;
(3) in another reactor with united catalyst cuprous bromide 15mg and 2,2-connects pyridine 20mg and adds to stir among the pore-foaming agent DMF and makes it to dissolve fully, obtains blue solution; Blue solution adds in the solution A and mixes, and obtains solution B;
(4) the logical nitrogen of solution B is 10 minutes, removes deoxidation and moisture; Reactor places 60 ℃ oil bath then, stirring reaction 24 hours; Centrifugation obtains containing the imprinted polymer magnetic composite nano particle of theophylline template molecule.
B. wash-out template molecule
The imprinted polymer magnetic composite nano particle that contains the theophylline molecule that (1) will prepare, with the chloroform dispersion of 5mL, solution becomes little yellow; Add methyl alcohol 10mL then, stirred centrifugation then 30 minutes;
(2) centrifugal gained solid is the mixed solution immersion of 1/9 (V/V) with acetate/methyl alcohol, vibrates 3 hours; Use the methyl alcohol cyclic washing until neutrality after the elimination soak, in 60 ℃, be dried to constant weight then with vacuum drying oven.
The molecularly imprinted polymer composite magnetic nano particle of prepared shell/nuclear structure, shell is a theophylline imprinted polymer layer, its size Control is at 15nm; Nuclear is MnFe
2O
4Magnetic material, MnFe
2O
4Content is 69.1%; Because contrast molecule, its separation factor to theophylline is 8.16 with coffee.
Embodiment 2.
A. imprinted templates molecule
(1) with Fe
3O
4It is in the aqueous solution of 0.5mol/L that magnetic powder nanometer powder (9nm) 25mg joins the concentration that contains ATRP initiator B MPA, the ultrasonic dispersion of water-bath 60 minutes, and solution becomes little yellow; In above-mentioned solution, add hydrochloric acid and make the pH value maintain 5, and be transferred in the reactor that has blender, stirred 24 hours; Stirring stops the back centrifugation, obtains the magnetic nanoparticle of yellowish BMPA functionalization, is washed with water to neutral and dry;
(2) the magnetic nanoparticle of functionalization adds in the reactor, adds function monomer 4-vinylpridine 1mmol, template molecule caffeine 20mg, crosslinking agent DVB 5mmol successively, stirs to make it to dissolve fully, obtains translucent viscous solution A;
(3) in reactor with united catalyst stannous chloride 15mg and 4,4-two-nonyl-2,2-connect pyridine 40mg and add to stir among the pore-foaming agent DMSO and makes it to dissolve fully, solution becomes blueness; Add solution A then and mix, obtain solution B;
(4) the logical nitrogen of solution B is 30 minutes, removes deoxidation and moisture; Reactor places 100 ℃ oil bath then, stirring reaction 20 hours; Centrifugation obtains containing the imprinted polymer magnetic composite nano particle of caffeine template molecule.
B. wash-out template molecule
The imprinted polymer magnetic composite nano particle that contains caffeine molecule that (1) will prepare, with the chloroform dispersion of 5mL, solution becomes little Huang; Add methyl alcohol 100mL then, stirred centrifugation afterwards 30 minutes;
(2) centrifugal gained solid is that 1/9 mixed solution soaks with acetate/methyl alcohol volume ratio, vibrates 30 minutes; Use the methyl alcohol cyclic washing until neutrality after the elimination soak, in 100 ℃, be dried to constant weight then with vacuum drying oven.
The molecular engram polymer magnetic composite nano particles of prepared shell/nuclear structure, shell are caffeine imprinted polymer layer, and its size Control is at 13nm; Nuclear is Fe
3O
4Magnetic material, Fe
3O
4Content is 77.5%, is the contrast molecule with the theophylline, and its separation factor to caffeine is 7.83.
Embodiment 3.
A. imprinted templates molecule
(1) with Fe
2O
3It is in the aqueous solution of 2mol/L that magnetic powder nanometer powder (9nm) 25mg joins the concentration that contains ATRP initator monobromo-acetic acid, the ultrasonic dispersion of water-bath 30 minutes, and solution becomes little yellow; In above-mentioned solution, add hydrochloric acid and make the pH value maintain 4, and be transferred in the reactor that has blender, stirred 48 hours; Stirring stops the back centrifugation, obtains the magnetic nanoparticle of yellowish monobromo-acetic acid functionalization, is washed with water to neutral and dry;
(2) the magnetic nanoparticle of functionalization adds in the reactor, adds function monomer 4-vinylpridine 1mmol, template molecule ethyl parathion 20mg, crosslinking agent DVB5mmol successively, stirs to make it to dissolve fully, obtains translucent viscous solution A;
(3) in reactor with united catalyst stannous chloride 15mg and 4,4-two-tertiary butyl-2,2-connect arsenic pyridine 50mg and add to stir in the pore-foaming agent toluene and makes it to dissolve fully, solution becomes blueness; Add solution A then and mix, obtain solution B;
(4) the logical nitrogen of solution B is 60 minutes, removes deoxidation and moisture; Reactor places 50 ℃ oil bath then, stirring reaction 48 hours; Centrifugation obtains containing the imprinted polymer magnetic composite nano particle of ethyl parathion template molecule.
B. wash-out template molecule
The imprinted polymer magnetic composite nano particle that contains the ethyl parathion molecule that (1) will prepare, with the chloroform dispersion of 5mL, solution becomes little yellow, adds methyl alcohol 100mL then, stirs centrifugation then 100 minutes;
(2) centrifugal gained solid is that 9/1 mixed solution soaks with acetate/methyl alcohol volume ratio, vibrates 60 minutes; Use the methyl alcohol cyclic washing until neutrality after the elimination soak, in 80 ℃, be dried to constant weight then with vacuum drying oven.
The molecular engram polymer magnetic composite nano particles of prepared shell/nuclear structure, shell are ethyl parathion imprinted polymer layer, and its size Control is at 18nm; Nuclear is Fe
2O
3Magnetic material, Fe
2O
3Content is 57.3%, is the contrast molecule with the parathion-methyl, and its separation factor to ethyl parathion is 5.68.
Embodiment 4.
A. imprinted templates molecule
(1) with MnFe
2O
4It is in the aqueous solution of 0.5mol/L that magnetic powder nanometer powder (9nm) 25mg joins the concentration that contains ATRP initator 3-bromo-propionic acid, the ultrasonic dispersion of water-bath 100 minutes, and solution becomes little yellow; In above-mentioned solution, add hydrochloric acid and make the pH value maintain 4, and be transferred in the reactor that has blender, stirred 50 hours; Stirring stops the back centrifugation, obtains the magnetic nanoparticle of yellowish 3-bromo-propionic acid functionalization, is washed with water to neutral and dry;
(2) the magnetic nanoparticle of functionalization adds in the reactor, add function monomer trifluoromethyl acrylate 1mmol, template molecule dopamine (norepinephrine precursor) 20mg, crosslinking agent EGDMA5mmol successively, stirring makes it to dissolve fully, obtains translucent viscous solution A;
(3) in reactor with united catalyst cuprous bromide 15mg and 4,4-two-n-heptyl-2,2-connect arsenic pyridine 100mg and add to stir in the pore-foaming agent oxolane and makes it to dissolve fully, solution becomes blueness; Add solution A then and mix, obtain solution B;
(4) the logical nitrogen of solution B is 60 minutes, removes deoxidation and moisture; Reactor places 50 ℃ oil bath then, stirring reaction 18 hours; Centrifugation obtains containing the imprinted polymer magnetic composite nano particle of dopamine template molecule.
B. wash-out template molecule
The imprinted polymer magnetic composite nano particle that contains the dopamine molecule that (1) will prepare, with the chloroform dispersion of 5mL, solution becomes little yellow; Add methyl alcohol 5mL then, stirred centrifugation then 20 minutes;
(2) centrifugal gained solid is that 1/9 mixed solution soaks with acetate/methyl alcohol volume ratio, vibrates 120 minutes; Use the methyl alcohol cyclic washing until neutrality after the elimination soak, in 50 ℃, be dried to constant weight then with vacuum drying oven.
The molecular engram polymer magnetic composite nano particles of prepared shell/nuclear structure, shell are dopamine imprinted polymer layer, and its size Control is at 12nm; Nuclear is MnFe
2O
4Magnetic material, MnFe
2O
4Content is 80.5%, is the contrast molecule with the norepinephrine, and its separation factor to dopamine is 3.79.
Claims (8)
1. size controllable molecular engram polymer magnetic composite nano particles, comprise template molecule is had the polymer shell of single-minded recognition capability and the nuclear of nano particle, it is characterized in that the polymer shell is the imprinted polymer layer of controllable size, the nuclear of nano particle is magnetic nanometer powder.
2. size controllable molecular engram polymer magnetic composite nano particles as claimed in claim 1, the size that it is characterized in that the imprinted polymer shell is by the control of atom transition free radical polymerization reaction time.
3. size controllable molecular engram polymer magnetic composite nano particles as claimed in claim 1 is characterized in that nuclear is the ferromagnetic nano powder.
4. size controllable molecular engram polymer magnetic composite nano particles as claimed in claim 1, the template molecule that it is characterized in that described polymer shell be theophylline, caffeine, ethyl parathion or dopamine molecule one of them.
5. as claim 1 or 3 described size controllable molecular engram polymer magnetic composite nano particles, the nuclear that it is characterized in that nano particle is MnFe
2O
4, Fe
3O
4Perhaps Fe
2O
3The magnetic material of one of them.
6. the preparation method of a size controllable molecular engram polymer magnetic composite nano particles may further comprise the steps:
A. imprinted templates molecule
(1) magnetic nanometer powder is joined in the aqueous solution that initiator concentration is 0.5～2mol/L, the ultrasonic dispersion of water-bath did not have precipitation to solution in 5～120 minutes and exists; In above-mentioned solution, add hydrochloric acid again and make the pH value maintain 4～6, and be transferred in the reactor that has blender, stirred 1～72 hour; Stirring stops the back centrifugation, obtains the magnetic nanoparticle of initator functionalization, is washed with water to neutral and dry;
(2) magnetic nanoparticle with above-mentioned functionalization adds in the reactor, adds function monomer, template molecule, crosslinking agent successively, stirs to make it to dissolve fully, obtains translucent viscous solution A;
(3) in the another one reactor united catalyst is added in the pore-foaming agent, stirring makes it to dissolve fully; Add solution A then and mix, obtain solution B;
(4) the logical nitrogen of solution B is 1～60 minute, removes deoxidation and moisture; Reactor places 50～120 ℃ oil bath then, stirring reaction 1～72 hour; Centrifugation obtains containing the imprinted polymer magnetic composite nano particle of template molecule;
B. wash-out template molecule
The imprinted polymer magnetic composite nano particle that contains template molecule that (1) will prepare, being dispersed to solution with the chloroform of 5～100mL does not have precipitation and exists; Add methyl alcohol 5～100mL then, stir centrifugation afterwards in 5～120 minutes;
(2) centrifugal gained solid is that 10/1～1/10 mixed solution soaks with acetate/methyl alcohol volume ratio, vibrates 1～72 hour; Use the methyl alcohol cyclic washing until neutrality after the elimination soak, in 50～120 ℃, be dried to constant weight then, promptly obtain size controllable molecular engram polymer magnetic composite nano particles with vacuum drying oven.
7. the preparation method of size controllable molecular engram polymer magnetic composite nano particles as claimed in claim 6 is characterized in that described initator is halopropanoic acid, halogenated acetic acids, 2 bromo 2 methyl propionic acid.
8. the preparation method of size controllable molecular engram polymer magnetic composite nano particles as claimed in claim 6 is characterized in that described catalyst is cuprous halide and the united catalyst that connects arsenic pyridine class.
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| CN101101282B (en) * | 2007-06-11 | 2011-06-08 | 中山大学 | Microwave assisted molecular blotting magnetic microsphere preparation method and uses |
| CN101308066B (en) * | 2008-06-12 | 2010-07-28 | 济南大学 | Trace amount mycotoxins molecular blotting column preparation method and application |
| CN104819884B (en) * | 2015-05-13 | 2017-07-14 | 湖南农业大学 | The pre-treating method of finished tea sample in the residual detection of dicofol agriculture |
| CN105542075B (en) * | 2015-11-27 | 2017-11-14 | 佛山科学技术学院 | The preparation method of AAO MIP nanotube films |
| CN105754053B (en) * | 2016-03-23 | 2018-05-29 | 广东省工程技术研究所 | A kind of preparation method of the magnetic mesoporous silicon substrate microballoons of MIP |
| CN105854843B (en) * | 2016-06-06 | 2018-10-16 | 大连理工大学 | A kind of preparation method of magnetic molecularly imprinted nano material |
| CN106947038B (en) * | 2017-04-07 | 2018-09-07 | 中国农业科学院农业质量标准与检测技术研究所 | Molecular imprinting stirring rod and preparation method thereof |
| CN109847721A (en) * | 2019-01-16 | 2019-06-07 | 南昌航空大学 | A kind of preparation method of the surface imprinted microballoon of superparamagnetism perfluoro octane sulfonate |
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| CN1390861A (en) * | 2002-06-26 | 2003-01-15 | 天津大学 | Magnetic composite microsphere of molecular blot polymer and its preparing process by combination of reverse-phase emulsion polymerization with suspension polymerization |
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| CN1390861A (en) * | 2002-06-26 | 2003-01-15 | 天津大学 | Magnetic composite microsphere of molecular blot polymer and its preparing process by combination of reverse-phase emulsion polymerization with suspension polymerization |
| CN1390863A (en) * | 2002-06-26 | 2003-01-15 | 天津大学 | Magnetic composite microsphere of molecular blot polymer and its suspemsion polymerization process for preparing it |
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