CN1193383C - Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method - Google Patents
Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method Download PDFInfo
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- CN1193383C CN1193383C CNB031113516A CN03111351A CN1193383C CN 1193383 C CN1193383 C CN 1193383C CN B031113516 A CNB031113516 A CN B031113516A CN 03111351 A CN03111351 A CN 03111351A CN 1193383 C CN1193383 C CN 1193383C
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- nano particle
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Abstract
The present invention relates to a magnetic core shell particle having the strong magnetic field response capability and a preparation method thereof, which belongs to the field of magnetic material. The internal core of the particle is a magnetic ferrite nanometer particle having superparamagnetism, the external core is silicon dioxide, and each particle is coated with 20 to 1000 magnetic ferrite particles. The preparation method comprises that ferrite particles are prepared by a coprecipitation method; the washed ferrite particles are directly dispersed into water-soluble inorganic salt water solution containing SiO#-[2] without any surface processing to be stirred, and the silicon dioxide coating of the first time is carried out; the silicon dioxide coating for the second time is carried out by a tetraethyl orthosilicate hydrolysis reaction. The present invention has the advantages of simple technology process and devices, high content of magnetic substances of the magnetic core shell particles, strong response capability of an external magnetic field, compact structure of a coating layer, no naked magnetic particles, good dispersancy in water, and easy further functionalization. The present invention is suitable for separation and purification of biological material and medicine products, and the particle of the present invention can be used as a magnetic-control directional conveying carrier of biological molecules and medicine molecules.
Description
Technical field
The invention belongs to field of magnetic material, particularly a kind of core-shell type magnetic particulate and preparation method thereof.
Background technology
Magnetic particle biomaterial such as cell, protein, DNA and RNA etc. separate and biological and medical fields such as purifying, biomolecular labeling and detection, immunoassay and targeted drug in application more and more widely.This mainly is based on the external magnetic field responding ability of magnetic particle, such as enrichment under the magnetic particle outside magnetic field and directed movement.Compare with separation method such as the precipitation method, centrifugal process, ion-exchange and various chromatography methods commonly used, the magnetic separation technique that grows up based on the enrichment under the effect of magnetic particle outside magnetic field has convenient and swift, characteristics such as equipment needed thereby is simple, extraction efficiency height.And with magnetic particle as pharmaceutical carrier, can realize the orientation conveying of medicine by the effect of external magnetic field, medicine is directly delivered to diseased region, can improve curative effect greatly, reduce side effects of pharmaceutical drugs, on some major diseases such as treatment for cancer, have a wide range of applications.In the existing commodity, mostly magnetic particle is the polymer microsphere that makes by emulsion polymerization or suspension polymerization.This polymer microsphere is made up of the magnetic core and the surface aggregate thing coating layer of inside; the general more complicated of its synthesis technique; use some poisonous organic solvent or polymerization single polymerization monomers through regular meeting in synthetic, microballoon is in case formation is difficult to it be carried out other finishing again.In addition, because what constitute polymer microsphere surface is some organic polymers, its biocompatibility is relatively poor, can't use in vivo, and the structure of these polymer covering layers is more loose usually, cause the leakage of internal magnetization particle easily, the magnetic particle of leakage has limited its range of application to the toxic effect of a lot of bioactivators.
The prior art that is close most with the present invention is that (Langmuir 1994 for one piece of document " Magnetic Silica Dispersons:Preparation and Stability ofSurface-Modified Silica Particles with a Magnetic Core " of delivering of Albert P.Philipse, 10,92～99) disclosed a kind of Fe in
3O
4-silica magnetic core-shell particle and preparation method thereof.Disclosed Fe with magnetic responsiveness ability
3O
4-silica core-shell particulate is that its kernel is the magnetic Fe with superparamagnetism
3O
4Nano particle, skin are silicon dioxide, have 6 or be less than 6 magnetic Fe in the coated with silica layer
3O
4Nano particle.The method of making this magnetic particle has the following steps: the preparation magnetic Fe
3O
4---surface treatment---coating of inorganic silicon source---organosilicon source coats nano particle.Said preparation magnetic Fe
3O
4Nano particle is to adopt known coprecipitation.Said surface treatment is to use Tetramethylammonium hydroxide to make peptizing agent, to magnetic Fe
3O
4Nano particle carries out peptization to be handled.It is with Na that said inorganic silicon source coats
2SiO
3Do the silicon source, the magnetic Fe after peptization is handled
3O
4Nano particle is put into Na
2SiO
3Fully stir in the aqueous solution, form SiO
2Coat Fe
3O
4Nano particle, the about 1nm of the thickness of coating layer.It is to do the silicon source with tetraethoxysilane that said organosilicon source coats, and is solvent with ethanol, and the concentrated ammonia liquor that with the mass percent concentration is 25-28% is that catalyst adds the magnetic Fe that coats through the inorganic silicon source
3O
4Stir behind the nano particle, prepare Fe
3O
4-silica core-shell particulate.Will be in the preparation process by the magnetic Fe of dialysis to coating through the inorganic silicon source
3O
4Nano particle is purified, the Fe for preparing at last
3O
4-silica core-shell particulate will be purified with the magnetic splitter of special use.
The Fe of background technology
3O
4The coating layer of-silica core-shell particulate is inorganic silicon dioxide, thereby particulate has excellent biological compatibility, better chemical stability, and can carry out various finishinges by different silylating reagents, the particulate after modified can combine with various biomaterials.But because this Fe
3O
4The magnetic Fe that coats in particle-silica core-shell particulate
3O
4Nano particle has only 6 or be less than 6, the magnetic kernel number very little, particulate magnetic a little less than, a little less than the external magnetic field responding ability, need to use special-purpose magnetic splitter and apply the enrichment that the high strength external magnetic field could realize this particle, this has just limited the application of this magnetic particle.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art exactly, proposes a kind of magnetic ferrites-silica core-shell particulate with high-intensity magnetic field responding ability and preparation method thereof.This magnetic ferrites-silica core-shell particulate has coenocytism, magnetisable material content height, has very strong external magnetic field responding ability, do not need special-purpose magnetic splitter just can realize the fast enriching of particulate under lower magnetic field intensity, coated with silica densification simultaneously, chemical stability be good, do not have exposed magnetic particle, the easy functionalization in surface; Do not need among the preparation method that the magnetic ferrites nano particle is carried out peptization and handle, technical process is simpler, and equipment needed thereby is because particulate magnetic also becomes simple by force.
Magnetic ferrites-silica core-shell particulate with high-intensity magnetic field responding ability of the present invention, its kernel is the magnetic ferrites nano particle of coated with silica, shell is a silicon dioxide.Said magnetic ferrites nano particle refers to Fe
3O
4Nano particle, γ-Fe
2O
3Nano particle or mix transition metal and the magnetic ferrites nano particle of compound, they have superparamagnetism, and particle diameter is 3～12nm.Described particulate has coenocytism, and particle diameter is 0.2～10 μ m, is surrounded by 20～1000 magnetic ferrites nano particles in each particulate.The quality percentage composition of magnetic ferrites nano particle is 10～60% in the particulate.
The magnetic responsiveness ability of described particulate is: to the hydrosol of this core-shell particle of 10ml, under the externally-applied magnetic field of 0.05T, the particle enrichment time is in 1 minute.Can see that by transmission electron microscope the number of the magnetic ferrites nano particle that this core-shell particle with high-intensity magnetic field responding ability contains is 20～1000.
Preparation method with magnetic ferrites-silica core-shell particulate of high-intensity magnetic field responding ability of the present invention, the technical process that has preparation magnetic ferrites nano particles---coating of inorganic silicon source---organosilicon source to coat.That is:
At first utilize known coprecipitation to prepare the magnetic ferrites nano particle, the particle diameter of the magnetic ferrites nano particle that makes can utilize tilt-pour process to carry out the pure water cleaning under permanent magnetic field and remove impurity at 3～12nm;
Washed magnetic ferrites nano particle directly is distributed to without any surface treatment contains SiO
2The aqueous solution of water-soluble inorganic salt in stir and carry out the coated with silica first time, be coated on the magnetic ferrites nanoparticle surface through current inorganic silicon source and form the thick silicon dioxide layer of 1～2nm, the magnetic ferrites nano particle that utilizes tilt-pour process that the inorganic silicon source is coated again under permanent magnetic field carries out the pure water cleaning and removes impurity;
The magnetic ferrites nano particle of coated with silica is distributed in the mixed solvent of alcohol and water to finishing for the first time, under alkali condition, carries out the coated with silica second time by the teos hydrolysis reaction.Can obtain being of a size of multinuclear magnetic ferrites-silica core-shell particulate of 0.2～10 μ m by the control of reaction condition.
Wherein said magnetic ferrites nano particle is meant the nanometer Fe with superparamagnetism
3O
4Particle, γ-Fe
2O
3Nano particle or mix transition metal and the magnetic ferrites nano particle of compound.
In aforesaid cladding process process, process conditions are to need control.When the inorganic silicon source coated, the concentration of magnetic ferrites nano particle was 0.05～25g/L in the reaction solution, SiO
2Concentration be 0.1～50g/L.The pH of reaction solution is transferred between 8～11.Mixing speed is to react 5～24 hours under the condition of 50～800rpm.When the organosilicon source coats, alcohol in the mixed solvent of alcohol and water can be methyl alcohol, ethanol, propyl alcohol, butanols etc., the volumn concentration of alcohol is 30～100% in the mixed solvent, the volumn concentration of water is 0～70%, the adding mass percent concentration is 25～28% concentrated ammonia liquor in above-mentioned solution, in the mixed solution of Xing Chenging, the concentration of magnetic ferrites nano particle is 0.05～1g/L thus, and the molar concentration of ammoniacal liquor in reaction solution is 0.5～1mol/L.Under the mixing speed of 50～500rpm, dropwise add tetraethoxysilane 0.5～5ml/L then, reacted 3～30 hours.
Dropwise adding tetraethoxysilane during above-mentioned organosilicon source coats, tetraethoxysilane can add in batches, and each addition is 0.5～1.5ml/L, and wherein the time interval of adjacent twice adding is 2～6h, after tetraethoxysilane all adds, continue reaction 3～24h again.By the addition of control tetraethoxysilane, can regulate the thickness of coated with silica layer of magnetic ferrites-silica core shell particles of last formation and the size of resulting core-shell particle.
The aforesaid tilt-pour process that utilizes under steady magnetic field cleans when removing impurity with pure water, can working strength be the permanent magnet of 0.05～0.15T.
As mentioned above, the present invention is under the reaction condition of gentleness, synthesized magnetic ferrites-silica core-shell particulate by simple technical process, this particulate has following characteristics: (1) magnetisable material content height, very strong external magnetic field responding ability is arranged, under very low external magnetic field effect, get final product rapid enrichment; (2) compact structure of coated with silica layer, thereby chemical stability height, oxidation resistance is strong; (3) do not have exposed magnetic particle, and good leak integrity is arranged; (4) Biao Mian chemical composition is a silicon dioxide, and easily further functionalization utilizes the silylating reagent that has groups such as amino, sulfydryl, epoxy that silica surface is modified, the surface of can obtain having amino, dredging functional groups such as base, epoxy.
Magnetic ferrites described in the invention-the good dispersion of silica core-shell particulate in water, can connect various bioactivators (as cell, antibody, antigen, enzyme or nucleic acid) and drug molecule after the surface is modified, be specially adapted to separating and purifying of various biomaterials and pharmaceutical products, and can be as biomolecule and the directed carrier of carrying of drug molecule magnetic control.
The preparation method of magnetic ferrites of the present invention-silica core-shell particulate, technical process is simple, and is lower to equipment requirements.
Embodiment
Embodiment 1:Fe
3O
4The preparation of nano particle
Take by weighing the FeCl of 27.45g
36H
2The FeCl of O and 10.10g
24H
2O, water-soluble the separating of passing through letting nitrogen in and deoxidizing with 100ml obtains mixed solution.Get 400ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 1L, the mass percent concentration that adds 25ml is the concentrated ammonia liquor of 25-28%, rapidly to wherein pouring above-mentioned molysite mixed solution into, reacts 1h down at 80 ℃ under vigorous stirring.After reaction finishes, isolate the solid of black with the permanent magnet of 0.1T from reaction solution, the gained solid promptly gets the Fe that particle diameter is 6～10nm 3～5 times with the high purity water cleaning
3O
4Nano particle.
Embodiment 2: γ-Fe
2O
3The preparation of nano particle
Take by weighing the FeCl of 27.45g
36H
2The FeCl of O and 10.10g
24H
2O, water-soluble the separating of passing through letting nitrogen in and deoxidizing with 100ml obtains mixed solution.Get 400ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 1L, the mass percent concentration that adds 25ml is the concentrated ammonia liquor of 25-28%, rapidly to wherein pouring above-mentioned molysite mixed solution into, reacts 1h down at 80 ℃ under vigorous stirring.Aerating oxygen 2h in reaction solution then.After reaction finishes, isolate red solid with the permanent magnet of 0.1T from reaction solution, the gained solid cleans with high purity water and promptly gets γ-Fe that particle diameter is 6～10nm 3～5 times
2O
3Nano particle.
Embodiment 3:CoFe
2O
4The preparation of nano particle
Take by weighing the CoCl of 27.86g
36H
2The FeCl of O and 10.10g
24H
2O, water-soluble the separating of passing through letting nitrogen in and deoxidizing with 100ml obtains mixed solution.Get 400ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 1L, the mass percent concentration that adds 25ml is the concentrated ammonia liquor of 25-28%, rapidly to wherein pouring above-mentioned mixing salt solution into, reacts 1h down at 50 ℃ under vigorous stirring.After reaction finishes, isolate the solid of black with the permanent magnet of 0.1T from reaction solution, the gained solid promptly gets the CoFe that particle diameter is 3～13nm 3～5 times with the high purity water cleaning
2O
4Nano particle.
Embodiment 4: the inorganic silicon source coats (coated with silica for the first time)
Take by weighing 2.5g Na
2SiO
3(SiO
2Content is 45%) be dissolved in the 500ml water, be 9.6 with the pH of resin cation regulator solution, to wherein adding the above-mentioned synthetic Fe of 1g
3O
4Nano particle.At room temperature, in the 1L round-bottomed flask, react 12h with the 150rpm mixing speed.After reaction finishes, isolate the solid of black with the permanent magnet of 0.1T from reaction solution, the gained solid promptly gets the Fe that particle diameter is the coated with silica of 7～12nm 3～5 times with the high purity water cleaning
3O
4Nano particle.
Embodiment 5: the organosilicon source coats (coated with silica for the second time)
The concentrated ammonia liquor, 0.05g that add 450ml ethanol, 50ml water, 20ml mass percent concentration successively and be 25-28% in the 1L round-bottomed flask are through the synthetic Fe of the coated with silica first time
3O
4Nano particle.At room temperature, drip the 0.3ml tetraethoxysilane, drip the 0.3ml tetraethoxysilane again behind the reaction 3h, continue reaction 12h with the 200rpm mixing speed.Isolate the solid of black with the permanent magnet of 0.1T from reaction solution, the gained solid cleans with high purity water and promptly gets the multinuclear Fe that average-size is 0.4 μ m 3～5 times
3O
4-SiO
2Core-shell particle.
Get above-mentioned core-shell particle 0.330g and be dispersed among the 10ml 1M HCl and soak 10min, the iron concentration of leakage is 4ppm; Get above-mentioned core-shell particle 0.030g and be dispersed in the 1ml water, under the magnetic field of 0.05T, the enrichment time of particulate is 10s; Get above-mentioned core-shell particle 0.030g and be dispersed in 1ml 50%HNO
3In, behind the heating 24h, under the magnetic field of 0.5T, the enrichment time of particulate still is 10s in 95 ℃ of water-baths.
Embodiment 6: with the nanometer Fe in embodiment 4,5 processes
3O
4Particle changes γ-Fe into
2O
3And/or CoFe
2O
4Nano particle, the preparation process of employing embodiment 4,5 can make γ-Fe
2O
3-silica core-shell particulate and/or CoFe
2O
4-silica core-shell particulate.
Claims (4)
1, a kind of magnetic core-shell particle with high-intensity magnetic field responding ability, its kernel is the magnetic ferrites nano particles, shell is a silicon dioxide, it is characterized in that, is coated with 20～1000 magnetic ferrites nano particles in each particulate; The quality percentage composition of magnetic ferrites nano particle is 10～60% in the particulate.
2, according to the described magnetic core-shell particle of claim 1, it is characterized in that the particle diameter of magnetic ferrites nano particle is 3～12nm with high-intensity magnetic field responding ability; The capsomeric particle diameter of magnetic core is 0.2～10 μ m.
3, according to claim 1 or 2 described magnetic core-shell particles with high-intensity magnetic field responding ability, it is characterized in that its magnetic responsiveness ability is: to the hydrosol of this core-shell particle of 10ml, under the externally-applied magnetic field of 0.05T, the particle enrichment time is in 1 minute.
4, a kind of capsomeric preparation method of magnetic core with high-intensity magnetic field responding ability, said magnetic core-shell particle, kernel is the magnetic ferrites nano particles, and shell is a silicon dioxide, is coated with 20～1000 magnetic ferrites nano particles in each magnetic core-shell particle; The quality percentage composition of magnetic ferrites nano particle is 10～60% in the particulate; The technical process that has preparation magnetic ferrites nano particle, the coating of inorganic silicon source, organosilicon source to coat; At first utilize known coprecipitation to prepare the magnetic ferrites nano particle, then the magnetic ferrites nano particle is carried out twice coating with inorganic silicon source and organosilicon source; With Na
2SiO
3Do the inorganic silicon source, it is characterized in that, the magnetic ferrites nano particle carry out the inorganic silicon source coat before without any surface treatment; When the inorganic silicon source coated, the concentration of magnetic ferrites nano particle was 0.05～25g/L in the reaction solution, SiO
2Concentration be 0.1～50g/L, the pH value of reaction solution is 8～11, mixing speed is to react 5～24 hours under the condition of 50～800rpm; When the organosilicon source coats, the volumn concentration of alcohol is 30～100% in the mixed solvent of alcohol and water, the volumn concentration of water is 0～70%, the adding mass percent concentration is 25～28% concentrated ammonia liquor in above-mentioned solution, in the mixed solution of Xing Chenging, the concentration of magnetic ferrites nano particle is 0.05～1g/L thus, and the molar concentration of ammoniacal liquor is 0.5～1mol/L, under the mixing speed of 50～500rpm, dropwise add tetraethoxysilane 0.5～5ml/L, reacted 3～30 hours.
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|---|---|---|---|
| CNB031113516A CN1193383C (en) | 2003-04-01 | 2003-04-01 | Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method |
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| CNB031113516A CN1193383C (en) | 2003-04-01 | 2003-04-01 | Magnetic hud fine particles possessing strong magnetic field response capability and its preparing method |
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| CN1193383C true CN1193383C (en) | 2005-03-16 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100505116C (en) * | 2004-11-19 | 2009-06-24 | 南京大学 | Fe/(SiO-[2]+C) core-shell composite nanometer particle with high stability and method for preparing same |
| CN100366532C (en) * | 2006-06-08 | 2008-02-06 | 复旦大学 | Silicon/oxidative silicon nuclear-shell structured nano-composite material, its preparation and use |
| CN100497186C (en) * | 2007-05-15 | 2009-06-10 | 中国科学院长春应用化学研究所 | Method for preparing Fe2O3 Nano particles clad by Fe2O3 |
| CN101318148B (en) * | 2007-06-06 | 2010-05-26 | 中国石油化工股份有限公司 | Method for preparation of spherical magnetic alumina support |
| CN101205420B (en) * | 2007-12-06 | 2012-01-18 | 复旦大学 | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof |
| CN101388267B (en) * | 2008-07-09 | 2011-04-13 | 长春市博坤生物科技有限公司 | Silicon dioxide magnetic composite particle and preparation |
| US8669354B2 (en) * | 2009-01-26 | 2014-03-11 | The Hong Kong Polytechnic University | Removal of endotoxin using amphiphilic core-shell nanosorbents |
| CN101597105B (en) * | 2009-06-11 | 2011-01-19 | 浙江省环境保护科学设计研究院 | Preparation method for magnetic carrier in processing technique of sewage biological fluidized bed |
| CN103834316B (en) * | 2012-11-26 | 2017-11-21 | 鸿富锦精密工业（深圳）有限公司 | Adhesive structure, surface conditioning agent and tear off method |
| CN107633946A (en) * | 2017-09-25 | 2018-01-26 | 常州市沃兰特电子有限公司 | A kind of preparation method of nanometer of magnet |
| BR112021000731A2 (en) * | 2018-07-19 | 2021-04-13 | Beckman Coulter, Inc. | MAGNETIC PARTICLES |
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